O-iminoisourea compounds, O-iminoisourea compound salts, O-iminoisourea complexes, thermal polymerization initiators, polymerizable compositions, cured products and methods for producing the same, methods for producing the O-iminoisourea compounds, O-iminoisourea compound salts or O-iminoisourea complexes, and methods for producing hydroxamate derivatives which are intermediates.

Abstract

This invention provides a novel O-iminoisourea compound that can function as a thermal polymerization initiator, etc. [Solution] The O-iminoisourea compound is represented by the following general formula (I). TIFF2026167655000056.tif44170 (In equation (I), n is an integer between 1 and 4, and R4 and R5 are monovalent organic groups.) If n=1, L 1、 L2 and L3 are monovalent organic groups. When n is between 2 and 4, one of L1 through L3 is an n-valent organic group, and the others are monovalent organic groups. L1, L2, L 3、 R4 and R5 may have one or more O, N, S, Si, or halogen atoms.

Description

Technical Field

[0001] The present invention relates to a novel O-iminoisourea compound, a novel O-iminoisourea compound salt, and an O-iminoisourea complex. The present invention also relates to a thermal polymerization initiator as an example of the use of these, a polymerizable composition containing the same, a cured product thereof and a method for producing the same, as well as a method for producing the aforementioned O-iminoisourea compound, O-iminoisourea compound salt or O-iminoisourea complex, and a method for producing a hydroxamate derivative which is an intermediate.

Background Art

[0002] Iminoisourea compounds are known to function as thermal polymerization initiators because they are stable at normal temperature and generate radicals when heated to exhibit polymerization activity. Therefore, for example, their use as thermal polymerization initiators has been studied in polymerizable compositions used for building materials, surface coating agents, curable inks, adhesives and the like, as well as in polymerizable compositions used for producing pixels and partition walls of image display devices such as liquid crystal displays and electroluminescent elements.

[0003] A thermal polymerization initiator generates initiating radicals for the polymerization reaction upon heating, enabling a curing reaction in a low temperature region. Examples of the thermal polymerization initiator include azo compounds, dialkyl peroxides, diacyl peroxides, hydroperoxides and the like. However, many conventionally used thermal polymerization initiators have low thermal stability, and there have been problems in their own production, storage and handling. Therefore, a thermal polymerization initiator that is safe and has good handleability is demanded. In addition, when a thermal polymerization initiator is used in the manufacture of electronic devices such as the aforementioned OLED display panels, high reactivity that allows the curing reaction to proceed at low temperatures is desirable in order to suppress thermal damage to the elements. Furthermore, it is desirable that no harmful components are generated during the heat treatment, and that components derived from the thermal polymerization initiator do not cause deterioration of electronic members.

[0004] Regarding iminoisourea compounds, for example, Patent Document 1 discloses the use of O-iminoisourea compounds or salts thereof as thermal polymerization initiators, and polymerizable compositions containing them. Patent Document 2 discloses a polymerizable composition comprising a monomer composition containing at least one ethylenically unsaturated monomer having a β-epithiopropyl functional group, a compound having two or more β-epithiopropyl functional groups but lacking polymerizable ethylenically unsaturated bonds, an isourea-functional polymerization initiator, and a catalyst acting on the reaction between β-epithiopropyl functional groups, wherein the isourea-functional polymerization initiator comprises at least one of O-dialkylamino-isourea and O-iminoisourea. Patent Document 3 discloses a polymerizable composition using a novel compound, which is an O-iminoisourea compound in which a sulfur atom is bonded to the imino group carbon, as a thermal polymerization initiator, a cured product obtained from this polymerizable composition, and a display device containing this cured product.

[0005] Non-patent document 4 reports on the polymerization reactivity of butyl acrylate and the initiator properties based on energy calculations of radical generation for O-iminoisoureas with different substituents on the imine and urea. Non-patent document 5 reports on the reactivity of a crosslinking and gelation reaction of methacrylate esters using O-iminoisourea as a thermal initiator and benzyl ketal as a photoinitiator, based on a kinetic analysis performed by tracking the reaction in infrared light. Non-patent document 6 describes a specific O-iminoisourea compound as an intermediate in a reaction when synthesizing another compound. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Special Publication No. 2012-526167 [Patent Document 2] Special Publication No. 2015-518077 [Patent Document 3] International Publication No. 2023 / 190410 [Non-patent literature]

[0007] [Non-Patent Document 4] J. Polym. Sci., Part A, Polym. Chem., 56, 1749-1756, 2018, Iminoisourea + Bu Acrylate Polymerization, DSC Evaluation, Substitution Effects [Non-Patent Document 5] Materials 2020, 13, 3277 Comparison of hydrogel reactions with isourea and benzyl ketal photoinitiators. [Non-Patent Document 6] Journal de la Societe Chimique de Tunisie (1986), 2(3), 9-13 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide novel O-iminoisourea compounds, salts and complexes thereof, methods for producing them, and applications for these novel O-iminoisourea compounds, salts and complexes thereof, which can function, for example, as thermal polymerization initiators. [Means for solving the problem]

[0009] To solve the above problems, the present invention proposes O-iminoisourea compounds, their salts and complexes in the following embodiments, methods for producing them, and applications for these new O-iminoisourea compounds, their salts and complexes.

[0010] [1] A first aspect of the present invention is an O-iminoisourea compound represented by the following general formula (I) (excluding the O-iminoisourea compound represented by the following structural formula (I)-A).

[0011] TIFF2026167655000001.tif59170

[0012] TIFF2026167655000002.tif44170

[0013] In equation (I), n is an integer between 1 and 4. R4 and R5 are monovalent organic groups. If n=1, L 1、 L2 and L3 are monovalent organic groups. If n is between 2 and 4, one of L1 to L3 is an n-valent organic group, and the others are monovalent organic groups. L1, L2, L 3、 R4 and R5 may have one or more O, N, S, Si, or halogen atoms.

[0014] [2] A second aspect of the present invention is an O-iminoisourea compound salt represented by the following general formula (II).

[0015] TIFF2026167655000003.tif51170

[0016] In equation (II), n is an integer between 1 and 4. R4 and R5 are monovalent organic groups. If n=1, L 1、 L2 and L3 are monovalent organic groups. If n is between 2 and 4, one of L1 to L3 is an n-valent organic group, and the others are monovalent organic groups. L1, L2, L 3、 R4 and R5 may have one or more O, N, S, Si, or halogen atoms. Y is hydrogen, or C1~C 10 It is an alkyl group. m+ and m- represent electric charge, where m is an integer between 1 and 4. X m-is one selected from the group consisting of halide ion, sulfate anion, hydrogen sulfate anion, tetrafluoroborate anion, alkylsulfonate anion, arylsulfonate anion, alkylcarboxylate anion, and arylcarboxylate anion, or a combination of two or more thereof, provided that the total valence is -m.

[0017] [3] A third aspect of the present invention is an O-iminoisourea complex represented by the following general formula (III).

[0018] TIFF2026167655000004.tif52170

[0019] In formula (III), n is an integer of 1 to 4, R4 and R5 are each a monovalent organic group. When n=1, L 1、 L2 and L3 are each a monovalent organic group, When n is 2 to 4, any one of L1 to L3 is an n-valent organic group, and the others are each a monovalent organic group. L1, L2, L 3、 R4 and R5 may each have one or more O, N, S, Si or halogen atoms. Z p is a compound having Lewis acidity, and is one selected from the group consisting of boron halides, aluminum halides, C1-C4 tri(alkyloxy)boric acid, C6-C 10 tri(aryloxy)boric acid, zinc chloride, and cuprous chloride, or a combination of two or more thereof. p represents the number of Z, and is an integer equal to or less than n.

[0020] [4] A fourth aspect of the present invention is the O-iminoisourea compound of the first aspect, the O-iminoisourea compound salt of the second aspect, or the O-iminoisourea complex of the third aspect, wherein the number of carbon atoms of each organic group of L1, L2, L 3、 R4 and R5 in the aforementioned formulas (I), (II), and (III) is 30 or less, respectively. [5] A fifth aspect of the present invention is an O-iminoisourea compound, O-iminoisourea compound salt, or O-iminoisourea complex of the fourth aspect, wherein n=1 in formulas (I), (II), and (III). [6] A sixth aspect of the present invention is an O-iminoisourea compound, O-iminoisourea compound salt, or O-iminoisourea complex of the fourth or fifth aspect, wherein L1 has 10 or fewer carbon atoms in formulas (I), (II), and (III). [7] A seventh aspect of the present invention is an O-iminoisourea compound, O-iminoisourea compound salt, or O-iminoisourea complex of any one of the fourth to sixth aspects, wherein L1 in formulas (I), (II), and (III) is a t-butyl group.

[0021] [8] An eighth aspect of the present invention is a thermal polymerization initiator comprising one or more of the following: an O-iminoisourea compound represented by general formula (I) (including the compounds excluded in the first aspect), an O-iminoisourea compound salt represented by general formula (II), and an O-iminoisourea complex represented by general formula (III). [8-1] An 8-1 aspect of the present invention is a thermal polymerization initiator of the 8th aspect, wherein n=1 in formulas (I), (II), and (III). [8-2] An aspect of the 8-2 present invention is a thermal polymerization initiator according to the 8th or 8-1 present invention, wherein the number of carbon atoms in L1 in formulas (I), (II), and (III) is 10 or less. [8-3] An aspect of the 8-3 present invention is a thermal polymerization initiator according to any one of the above 8, 8-1, and 8-2, wherein L1 in formulas (I), (II), and (III) is a t-butyl group.

[0022] [9] The ninth aspect of the present invention is a polymerizable composition comprising a thermal polymerization initiator according to any one of the eighth, eighth-1, eighth-2, and eighth-3 aspects and a polymerizable compound.

[10] A tenth aspect of the present invention is a polymerizable composition according to the ninth aspect, wherein the polymerizable compound comprises an acrylate compound or a methacrylate compound or both.

[11] An eleventh aspect of the present invention is a cured product of the polymerizable composition of the ninth or tenth aspect.

[0023]

[12] A twelfth aspect of the present invention is a method for producing a hydroxamate derivative which is an intermediate in the production of an O-iminoisourea compound represented by the general formula (I) of the first aspect (including compounds excluded in the first aspect), This method for producing a hydroxamate derivative involves reacting a compound represented by compound (1), shown by the following general formula, with a silylating agent shown by the following formula in the presence of a base to synthesize an oxime chloride silyl ether derivative of the following general formula (2), and then reacting the oxime chloride silyl ether derivative with a metal alkoxide shown by the following general formula (3) to synthesize a hydroxamate derivative shown by the following general formula (4).

[0024] TIFF2026167655000005.tif52170

[0025] L1 and L2 in formulas (1) to (4) are the same as L1 and L2 in formula (I). The leaving group in the formulas representing the silylating agent is an anionic leaving group. In the formulas representing the silylating agent and formula (2), R a , R b and R c Each of these is independent of C1~C 10 Alkyl alkyl groups, or C1-C 10 C6-C may be substituted with alkyl groups. 20 It is an aryl group.

[0026]

[13] A thirteenth aspect of the present invention is a method for producing an O-iminoisourea compound represented by the general formula (I) of the first aspect (including compounds excluded in the first aspect), This is a method for producing an O-iminoisourea compound, in which the hydroxamate derivative represented by the general formula (4) obtained by the production method of the 12th embodiment is reacted with a carbodiimide derivative to synthesize an O-iminoisourea compound in which L3 is hydrogen in the general formula (I).

[0027]

[14] A fourteenth aspect of the present invention comprises an O-iminoisourea compound represented by the general formula (I) of the first aspect (including compounds excluded in the first aspect) and an acidic compound or C1-C represented by the following formula. 10 This is a method for producing an O-iminoisourea compound salt, comprising reacting it with an alkyl halide compound YX to synthesize the O-iminoisourea compound salt represented by the general formula (II) in the second embodiment.

[0028] TIFF2026167655000006.tif55170

[0029]

[15] A fifteenth aspect of the present invention is a method for producing an O-iminoisourea complex, comprising reacting an O-iminoisourea compound represented by the general formula (I) of the first aspect (including compounds excluded in the first aspect) with a Lewis acid compound pZ represented by the following formula to synthesize an O-iminoisourea complex represented by the general formula (III) of the third aspect.

[0030] TIFF2026167655000007.tif52170

[0031]

[16] A sixteenth aspect of the present invention is a method for producing a cured product using one or more of the following as a thermal polymerization initiator: an O-iminoisourea compound represented by general formula (I) (including the compounds excluded in the first aspect), an O-iminoisourea compound salt represented by general formula (II), and an O-iminoisourea complex represented by general formula (III). [Effects of the Invention]

[0032] The O-iminoisourea compounds, O-iminoisourea compound salts, and O-iminoisourea complexes proposed in this invention are novel O-iminoisourea compounds, O-iminoisourea compound salts, and O-iminoisourea complexes that have not been previously known. These can be used, for example, as thermal polymerization initiators. In particular, the O-iminoisourea compounds of the present invention are not organic sulfur compounds, and therefore have the advantage of avoiding concerns about the generation of sulfur-derived odors when used as thermal polymerization initiators, making them suitable for use in electronic equipment applications, for example. Since the O-iminoisourea compound salts of the present invention are polar compounds, they can be easily dissolved or dispersed in water. This allows for the reduction of the amount of organic solvent used in the composition preparation process and the reduction of organic solvent vapors during the curing process, making them suitable for use as environmentally friendly materials. The O-iminoisourea complexes of the present invention allow for adjustment of the radical generation initiation temperature while maintaining the stability of the O-iminoisourea compounds. In particular, lowering the initiation temperature of the O-iminoisourea complexes is useful for thermal polymerization initiators with thermal stability. [Modes for carrying out the invention]

[0033] The present invention will be described below based on one embodiment. However, the present invention is not limited to this embodiment.

[0034] <O-iminoisourea compound of the present invention> An example of an embodiment of the present invention is an O-iminoisourea compound (referred to as "the O-iminoisourea compound of the present invention") which is a compound represented by the following general formula (I).

[0035] TIFF2026167655000008.tif44170

[0036] In equation (I), n is an integer between 1 and 4. It is preferable that n=1 for ease of composition.

[0037] If n=1, L1, L2, and L3 are each monovalent organic groups, with L1 being substituent R1 (also simply referred to as "R1"), L2 being substituent R2 (also simply referred to as "R2"), and L3 being substituent R3 (also simply referred to as "R3"). It is preferable that the number of carbon atoms in R1, R2, and R3 is 30 or less.

[0038] Of these, R1 preferably has 10 or fewer carbon atoms, and more preferably is a t-butyl group. In the O-iminoisourea compound of the present invention, when R1 is a t-butyl group, it undergoes sequential decomposition upon heating during the reaction, generating highly active methyl radicals, and thus exhibits high activity as a thermal polymerization initiator. In this invention, methyl radicals may also be referred to as "Me radicals."

[0039] For n=2 to 4, one of L1, L2, or L3 is a linker and is an n-valent organic group. The others, i.e., those that are not linkers, are monovalent organic groups and are the same as substituents R1, R2, and R3. In other words, If L1 is the linker, then L2 is the substituent R2, and L3 is the substituent R3. If L2 is the linker, then L1 is substituent R1 and L3 is substituent R3. If L3 is the linker, then L1 is substituent R1 and L2 is substituent R2.

[0040] For n=2 to 4 When L1, L2, and L3 are n-valent organic groups, it is preferable that the number of carbon atoms in each organic group is 30 or less, more preferably 20 or less, and more preferably 10 or less.

[0041] R4 and R5 are monovalent organic groups in all n. R4 and R5 preferably have 30 or fewer carbon atoms and may have one or more O, N, S, Si, or halogen atoms.

[0042] (R1) When n=1, L1, or R1, is a monovalent organic group selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, heteroaryl groups, C(O)-alkyl groups, and C(O)-aryl groups. R1 preferably has 30 or fewer carbon atoms, more preferably 10 or fewer, and is particularly preferably a butyl group. In particular, R1 is preferably configured such that a Me group capable of being converted to a Me radical is bonded to the carbon atom bonded to the oxygen (to which L1 in formula (1) is bonded), and two substituents are bonded to the carbon atom. Regardless of what these two substituents are, they are converted to decomposition products during the Me radical generation process. If the two substituents are substituents that generate a linear alkyl ketone during the Me radical generation process, they are preferable because they have low radical reactivity and do not cause side reactions with the Me radical. If one of the two substituents is a Me group, it is preferable because the probability of Me radical generation increases. Furthermore, if both substituents are Me groups, it is especially preferable because Me radical generation is guaranteed.

[0043] (R2) When n=1, L2, or R2, is a monovalent organic group selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, and heteroaryl groups. R2 preferably has 30 or fewer carbon atoms, more preferably 20 or fewer, and more preferably 10 or fewer.

[0044] Furthermore, R2 may form a ring structure containing an imino carbon atom together with -O-R1. When a ring structure is formed, the total number of carbon atoms derived from -O-R1 and R2 is 60 or less.

[0045] (R3) When n=1, L3, or R3, is a monovalent organic group selected from the group consisting of hydrogen, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, C(O)-alkyl group, and C(O)-aryl group. R3 preferably has 30 or fewer carbon atoms, more preferably 20 or fewer, and more preferably 10 or fewer.

[0046] (R 4、 R5) R 4、 Each R5 is independently selected from the group consisting of a monovalent organic group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, and a heteroaryl group. R4 and R5 preferably have 30 or fewer carbon atoms, more preferably 20 or fewer, and more preferably 15 or fewer.

[0047] (L1 when n=2) If n=2 and L1 is a linker, then L1 is a divalent organic group with 30 or fewer carbon atoms. Examples of divalent organic groups include alkylenes, alkenylenes, alkylylenes, cycloalkylenes, heterocycloalkylenes, arylenes, heteroarylenes, alkanedicarbonyls, alkenedicarbonyls, alkynedicarbonyls, aryldicarbonyls, heteroaryldicarbonyls, oxybisarylenes, thiobisarylenes, N-alkyl-N,N-bisarylenes, and bisarylenes bridged with heteroatoms such as N-aryl-N,N-bisarylenes.

[0048] (L2 when n=2) If n=2 and L2 is a linker, then L2 is a divalent organic group with 30 or fewer carbon atoms. Examples of divalent organic groups include heteroatom-bridged bisarylenes such as alkylenes, alkenylenes, alkynylenes, cycloalkylenes, heterocycloalkylenes, arylenes, heteroarylenes, oxybisarylenes, and thiobisarylenes.

[0049] (L3 when n=2) If n=2 and L3 is a linker, then L3 is a divalent organic group with 30 or fewer carbon atoms. Examples of divalent organic groups include alkylene, alkenylene, alkylylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, alkanedicarbonyl, alkenedicarbonyl, alkynedicarbonyl, aryldicarbonyl, and heteroaryldicarbonyl.

[0050] (L1 or L2 when n=3) If n=3 and L1 or L2 is a linker, then L1 or L2 is a trivalent organic group with 30 or fewer carbon atoms. Examples of trivalent organic groups include alkanetriyl, alkenetriyl, alkynetriyl, cycloalkanetriyl, heterocycloalkanetriyl, arenetriyl, heteroarenetriyl, alkyltricarbonyl, alkenetricarbonyl, alkynetricarbonyl, aryltricarbonyl, and heteroaryltricarbonyl.

[0051] (L3 when n=3) If n=3 and L3 is a linker, then L3 is a trivalent organic group with 30 or fewer carbon atoms. Examples of trivalent organic groups include alkanetriyl, alkenetriyl, alkynetriyl, cycloalkanetriyl, heterocycloalkanetriyl, arenetriyl, heteroarenetriyl, alkyltricarbonyl, alkenetricarbonyl, alkynetricarbonyl, aryltricarbonyl, and heteroaryltriacyl.

[0052] (L1 or L2 when n=4) If n=4 and L1 or L2 is a linker, then L1 or L2 is a tetravalent organic group with 30 or fewer carbon atoms. Examples of tetravalent organic groups include alkanetetrayl, alkenetetrayl, alkynetetrayl, cycloalkanetetrayl, heterocycloalkanetetrayl, arenetetrayl, heteroarenetetrayl, alkyltetracarbonyl, alkenetetracarbonyl, alkynetetracarbonyl, aryltetracarbonyl, heteroaryltetracarbonyl, and silanetetracarbonyl.

[0053] (L3 when n=4) If n=4 and L3 is a linker, then L3 is a tetravalent organic group with 30 or fewer carbon atoms. Examples of tetravalent organic groups include alkanetetrayl, alkenetetrayl, alkynetetrayl, cycloalkanetetrayl, heterocycloalkanetetrayl, arenetetrayl, heteroarenetetrayl, alkyltetracarbonyl, alkenetetracarbonyl, alkynetetracarbonyl, aryltetracarbonyl, and heteroaryltetracarbonyl.

[0054] However, the O-iminoisourea compounds of the present invention exclude the O-iminoisourea compound represented by the following structural formula (I)-A. The O-iminoisourea compound represented by the following structural formula (I)-A is described in Non-Patent Document 6: Journal de la Societe Chimique de Tunisie (1986), 2(3), 9-13.

[0055] TIFF2026167655000009.tif59170

[0056] <O-iminoisourea compound salt of the present invention> An example of an embodiment of the present invention is an O-iminoisourea compound salt (referred to as "the O-iminoisourea compound salt of the present invention") which is represented by the following general formula (II).

[0057] TIFF2026167655000010.tif51170

[0058] n, R in equation (II) 4、 R5, L1, L2, and L3 are n, R in formula (I) above. 4、 It is the same as R5, L1, L2, and L3. In particular, from the viewpoint of ease of synthesis and solubility in various solvents, it is preferable that n=1. Furthermore, R1 is preferably a t-butyl group. As will be described later, when the O-iminoisourea compound salt of the present invention is heated, it decomposes sequentially to generate highly active methyl radicals, which exhibit high activity as a thermal polymerization initiator. Therefore, R1 is preferably a t-butyl group.

[0059] Y is hydrogen, or C1~C 10 It is an alkyl group. m+ and m- represent electric charge, where m is an integer between 1 and 4. X m- This is one or more selected from the group consisting of halide ions, sulfate anions, bisulfate anions, tetrafluoroborate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, and aryl carboxylate anions, and the total valency should be -m.

[0060] <O-iminoisourea complex of the present invention> An example of an embodiment of the present invention is an O-iminoisourea complex (referred to as "the O-iminoisourea complex of the present invention"), which is represented by the following general formula (III).

[0061] TIFF2026167655000011.tif52170

[0062] n, R in equation (III) 4、 R5, L1, L2, and L3 are n, R in formula (I) above. 4、 It is the same as R5, L1, L2, and L3. In particular, from the viewpoint of ease of synthesis and solubility in various solvents, it is preferable that n=1. Furthermore, it is particularly preferable that R1 be a t-butyl group. As will be described later, when the O-iminoisourea complex of the present invention is heated, it decomposes sequentially to generate highly active methyl radicals, which exhibit high activity as a thermal polymerization initiator, so it is preferable that R1 be a t-butyl group.

[0063] Z p These are Lewis acidic compounds, including boron halides, aluminum halides, C1-C4 tri(alkyloxy)boric acid, and C6-C 10 It is one or more substances selected from the group consisting of tri(aryloxy)boric acid, zinc chloride, and cuprous chloride. p represents the number of Z, and is an integer less than or equal to n.

[0064] <Explanation of Organic Groups> In general formulas (I), (II), and (III), the "organic groups" represented by R1-R5 and L1-L3 can be any substituents as long as their total number of carbon atoms is 30 or less. Examples include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, heteroaryl groups, etc. Furthermore, each group may have one or more O, N, S, Si, or halogen atoms. Substituents having these atoms include halides represented by RF, R-Cl, R-Br, and RI, ethers represented by OR, thioethers represented by SR, monosubstituted amines represented by NH(R), disubstituted amines represented by N(R)2, monoacylamines represented by NHC(O)R, diacylamines represented by N[C(O)R]2, silyls represented by Si(R)3, ketones represented by C(O)-R, esters represented by C(O)OR and OC(O)R, carbonates represented by OC(O)-OR, primary amides represented by C(O)NH(R), secondary amides represented by C(O)N(R)2, sulfoxides represented by S(O)R, sulfones represented by S(O)2R, CN, NO2, and the like, where the substituent R is one of the alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, or heteroaryl groups.

[0065] <Explanation of substituents> In this invention, the terms "alkyl" or "alkyl group" typically refer to a saturated linear or branched hydrocarbon group having 1 to 30 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and n-octadecyl. Generally, branched alkyl groups are effective in improving the lipophilicity of compounds. 2-ethylhexyl is preferred because it is highly effective in imparting solubility to compounds and is readily available as a common chemical at low cost. In the present invention, alkyl groups may be interrupted by one or more groups selected from O, S, N-alkyl, N-aryl, C(O), C(O)O, and CC(O). When multiple O, S, N-alkyl, N-aryl, C(O), C(O)O, and OC(O) groups are present, they are usually isolated from each other by at least one methylene group. Examples of alkyl groups interrupted by one or more oxygen atoms include -CH2-O-CH3, -CH2CH2-O-CH2CH3, and -[CH2CH2O] y -CH3(y is 1-4), -(CH2CH2O) y These are CH2CH3 (where y is 1-4), -CH2-CH(CH3)-O-CH2-CH2CH3, -CH2-CH2CH(CH3)-O-CH2-CH2CH3, -CH2-CH2CH(CH3)-O-CH2CH3, -CH2-CH2CH(CH3)-O-CH3, and -CH2CH(CH3)-O-CH2CH3. Polyethylene glycol derivatives are used to improve solubility because they are soluble in both polar and nonpolar solvents. -[CH2CH2O]3-CH3 is particularly useful.

[0066] In this invention, the term "alkenyl" or "alkenyl group" typically refers to a monounsaturated or polyunsaturated linear or branched hydrocarbon group having 2 to 30 carbon atoms and one or more double bonds. Alkenyls having one double bond include, for example, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, and 2-methyl-2-propenyl. Alkadienyls having four or more carbon atoms and two double bonds at arbitrary positions include, for example, 1,3-butadienyl, 1,3-pentadienyl, hexa-1,4-dien-1-yl, hexa-1,4-dien-3-yl, hexa-1,4-dien-6-yl, hepta-1,4-dien-7-yl, hepta-1,5-dien-1-yl, etc.

[0067] In this invention, the terms "alkynyl" or "alkynyl group" refer to an unsaturated linear or branched hydrocarbon group having 2 to 30 carbon atoms and one or more triple bonds. Examples include ethenyl, propargyl (2-propyne-1-yl), 1-propyne-1-yl, 1-methylprop-2-in-1-yl, 2-butyne-1-yl, 3-butyne-1-yl, 1-pentin-1-yl, 3-pentin-1-yl, 4-pentin-1-yl, 1-methylbutyne-2-in-1-yl, 1-ethylprop-2-in-1-yl, etc.

[0068] In this invention, the terms "cycloalkyl" or "cycloalkyl group" refer to monocyclic or polycyclic aliphatic groups having typically 3 to 30 carbon atoms. Examples of monocyclic aliphatic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, with cyclopentyl and cyclohexyl being particularly preferred. Examples of polycyclic rings include perhydronaphthyl, adamantyl, bicyclo[1.1.1]pentyl, bicyclo[2.2.1]heptyl, bicyclo[4.2.2]decyl, bicyclo[2.2.2]octyl, bicyclo[3.3.0]octyl, bicyclo[3.3.2]decyl, bicyclo[4.4.0]decyl, bicyclo[4.3.1]decyl, bicyclo[4.2.1]nonyl, bicyclo[3.3.1]nonyl, and bicyclo[3.2.1]octyl. Cycloalkyls may be interrupted by one or more C(O) groups. An example of a cycloalkyl interrupted by one C(O) is 3-oxobicyclo[2.2.1]heptyl.

[0069] In this invention, the terms "heterocycloalkyl" or "heterocycloalkyl group" typically refer to monocyclic heterocyclic non-aromatic groups with 3 to 8 members, particularly 5, 6, 7, or 8 members, as well as bicyclic heterocyclic non-aromatic groups. The monocyclic and bicyclic non-aromatic groups described above may be saturated or unsaturated. Furthermore, the monocyclic and bicyclic heterocyclic non-aromatic groups described above usually contain one, two, three, or four heteroatoms selected from N, O, and S, particularly one or two heteroatoms, as ring members, in which case the S atoms as ring members may exist as S, SO, or SO2. Heterocycloalkyl groups may be interrupted by one or more C(O) groups, usually by one or two groups. Examples of saturated or unsaturated 3- to 8-membered non-aromatic heterocyclic groups include oxylanyl, oxetanyl, thietanyl, thietanyl-S-oxide (S-oxothietanyl), thietanyl-S-dioxide (S-dioxothietanyl), pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolidinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, dioxolenyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl Examples include thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, and thiadinyl. Examples of heterocyclic rings that also contain one or two carbonyl groups as ring members include pyrrolidine-2-onyl, pyrrolidine-2,5-dionyl, imidazolidin-2-onyl, oxazolidine-2-onyl, and thiazolidin-2-onyl.

[0070] In this invention, the terms "aryl" or "aryl group" usually refer to monovalent monocyclic aromatic groups and polycyclic aromatic groups having a ring carbon atom. Examples of monocyclic aromatic groups include phenyl. Examples of polycyclic aromatic groups include bicyclic, tricyclic, or tetracyclic aromatic groups, such as naphthyl, phenantrenyl, anthracenyl, or pyrenyl. Preferred examples of aryl groups are phenyl and naphthyl. The terms "aryl" or "aryl group" refer only to the basic structure exhibiting aromaticity, while derivatives with substituents refer to that basic structure. For example, the tolyl group (a methyl group bonded to a phenyl group), the methoxyphenyl group (a methoxy group bonded to a phenyl group), the chlorophenyl group (a chlorine group bonded to a phenyl group), and the trifluoromethylphenyl group (a trifluoromethyl group bonded to a phenyl group) are all substituted derivatives of the phenyl group.

[0071] In this invention, the terms "heteroaryl" or "heteroaryl group" usually refer to unsaturated monocyclic heterocyclic groups and polycyclic heterocyclic groups that are aromatic. Heteroaryls typically contain one or more carbon atoms as ring members, in addition to one, two, three, or four heteroatoms selected from N, O, and S as ring members. Examples of monocyclic heteroaromatic groups include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl or 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl or 5-isothiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazole)yl, 3- or 5-(1,2,4-oxa Examples include diazole)yl, 2- or 5-(1,3,4-thiadiazole)yl, 2- or 5-(1,3,4-thiadiazole)yl, 4- or 5-(1,2,3-thiadiazole)yl, 3- or 5-(1,2,4-thiadiazole)yl, 1H-, 2H- or 3H-1,2,3-triazole-4-yl, 1,3,4-triazole-2-yl, 2H-triazole-3-yl, 1H-, 2- or 4H-1,2,4-triazolyl, 1H- or 2H-tetrazolyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, and 2-pyrazinyl. Examples of polycyclic heterocyclic groups include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzooxathiazolyl, benzooxadiazolyl, benzothiadiazolyl, benzooxazinyl, quinolinyl, isoquinolinyl, purinyl, 1,8-naphthilidyl, pteridyl, pyrido[3,2-d]pyrimidyl, pyridoimidazolyl, carbazoyl, or acridinyl.

[0072] In the present invention, the terms "alkylene (or alkanediyl)" or "alkylene group (or alkanediyl group)" refer, in each case, to an alkyl group having carbon atoms as defined above, wherein one hydrogen atom at any position of the alkyl group is replaced by a further bonding site to form a divalent group. Therefore, C1~C 30 Examples of alkylenes include divalent branched or unbranched saturated aliphatic chains having 1 to 30 carbon atoms, such as -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH(CH3)CH2-, -CH2CH2CH2CH2-, -CH2CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH(CH3)-, and -CH2C(CH3)2CH2-.

[0073] In the present invention, the terms “alkylene” or “alkylene group” mean an alkylene chain having typically 1 to 30 carbon atoms as defined above, wherein two consecutive internal methylene groups of the alkylene chain are interrupted by O, S, N-alkyl, N-aryl, C(O), or C(S). The alkylene portion may contain, for example, one, two, three, four, five, or more than five identical or different groups selected from O, S, N-alkyl, N-aryl, C(O), and C(S). When multiple O, S, N-alkyl, N-aryl, C(O), or C(S) groups are present, they are not usually adjacent; that is, they are isolated from each other by at least one methylene group.

[0074] In the present invention, the terms "alkenylene (or alkenediyl)" or "alkenylene group (or alkenediyl group)" refer, in each case, to a linear or branched alkenyl group having typically 2 to 30, preferably 2 to 12, carbon atoms as defined above, wherein one hydrogen atom at any position on the carbon skeleton is replaced by a further bonding site to form a divalent portion. Therefore, C2~C 20 -Examples of alkenylenes include divalent linear or branched aliphatic chains having 2 to 30 carbon atoms, such as vinylene, propenylene, bute-1-enylene, bute-2-enylene, and penta-1,3-dieylene.

[0075] In the present invention, the terms "alkynylene (or alkynediyl)" or "alkynylene group (or alkynediyl group)" refer, in each case, to a linear or branched alkynyl group having typically 2 to 30, preferably 2 to 12, carbon atoms as defined above, wherein one hydrogen atom at any position on the carbon skeleton is replaced by a further bonding site to form a divalent portion.

[0076] In this invention, the terms "cycloalkylene" or "cycloalkylene group" refer to a cycloalkyl group as defined above, wherein one hydrogen atom at any position of the cycloalkyl group is replaced by a further bonding site to form a divalent group. In the case of polycyclic cycloalkylenes, their bonding sites are located either within the same ring or within different rings. Examples of monocyclic rings include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, or cycloheptylene, and especially cyclohexylene. Examples of polycyclic rings include perhydroanthrasilene, perhydronaphthylene, perhydrofluorenylene, perhydrocricenylene, perhydropicenylene, adamantylene, bicyclo[1.1.1]pentylene, bicyclo[2.2.1]heptylene, bicyclo[4.2.2]decylene, bicyclo[2.2.2]octylene, bicyclo[3.3.2]decylene, bicyclo[4.3.2]undecylene, bicyclo[4.3.3]dodecylene, bicyclo[3.3.3]undecylene, bicyclo[4.3.1]decylene, bicyclo[4.2.1]nonylene, bicyclo[3.3.1]nonylene, and bicyclo[3.2.1]octylene. The cycloalkylene may be substituted with one or more substituents, for example, C1-C4 alkyl groups.

[0077] In this invention, the term "arylene (also called arenediyl)" or "arylene group" refers to an aryl group as defined above, wherein one hydrogen atom at any position on the aryl group is replaced by a further bonding site to form a divalent group. In the case of polycyclic arylenes, these bonding sites are located either in the same ring or in different rings. Examples of arylenes are phenylene, naphthylene, anthracenediyl, or phenantrendiyl. When an arylene is substituted with one or more substituents, it may be, for example, monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or pentasubstituted, or more than pentasubstituted.

[0078] In this invention, the terms "heteroarylene" or "heteroarylene group" refer to a heteroaryl group as defined above, wherein one hydrogen atom at any position on the heteroaryl group is replaced by another bonding site to form a divalent group. In the case of polycyclic heteroarylenes, their bonds are located either within the same ring or in different rings. Heteroarylenes may be C-linked or N-linked, if possible. For example, pyrrolediyl, imidazolediyl, or pyrazolediyl may be N-linked or C-linked. Examples of heteroarenediyls are pyridinediyl, pyrimidinediyl, pyridazinediyl, 1,2,3-triazinediyl, 1,2,4-triazinediyl, 1,2,3,4-tetrazindiyl, franziyl, thiophenediyl, pyrrolediyl, thiazolediyl, thiadiazolediyl, pyrazolediyl, imidazolediyl, triazolediyl, oxazolediyl, isoxazolediyl, isothiazolidil, and oxadiazolediyl. Heteroarenediyls may be substituted with one or more substituents.

[0079] In this invention, the term "alkantriyl" or "alkantriyl group" refers to an alkylene group as defined above, which usually has 1 to 30 carbon atoms, and in which one hydrogen atom at any position of the alkylene is replaced by one further bonding site to form a trivalent group. Therefore, an alkantriyl is a trivalent, branched or unbranched, saturated aliphatic chain. An alkantriyl may be substituted with one or more substituents.

[0080] In this invention, the term "alkenediyl" or "alkenediyl group" refers to an alkenediyl group as defined above, which usually has 2 to 30 carbon atoms, and which forms a trivalent group when one hydrogen atom at any position of the alkenediyl is replaced by an additional bonding site. Therefore, an alkentriyl is a trivalent, branched or unbranched, unsaturated aliphatic chain. An alkentriyl may be substituted with one or more substituents.

[0081] In this invention, the term "alkyndiyl" or "alkyndiyl group" refers to an alkynediyl group as defined above, which usually has 2 to 30 carbon atoms, and which forms a trivalent group when one hydrogen atom at any position of the alkynediyl is replaced by an additional bonding site. Therefore, alkyntriyls are trivalent, branched or unbranched, unsaturated aliphatic chains. Alkyntriyls may be substituted with one or more substituents.

[0082] In this invention, the terms "cycloalkanetriyl" or "cycloalkanetriyl group" refer to a cycloalkylene group as defined above, wherein one hydrogen atom at any position of the cycloalkylene is replaced by another bonding site to form a trivalent group. In the case of polycyclic cycloalkanetriyls, their bonding sites are located either within the same ring or in different rings. Cycloalkanetriyls may be substituted with one or more substituents.

[0083] In this invention, the terms "arenetriyl" or "arenetriyl group" refer to an arylene group as defined above, wherein one hydrogen atom at any position on the arylene group is replaced by another bonding site to form a trivalent group. In the case of polycyclic arenetriyls, their bonds are located either within the same ring or in different rings. Examples of arenetriyls include 1,2,4-benzenetriyl, 1,3,5-benzenetriyl, 1,3,5-naphthalentriyl, 1,4,5-naphthalendiyl, anthracenatetriyl, or phenanthrentriyl. Arenetriyls may be substituted with one or more substituents.

[0084] In this invention, the terms "heterearene triyl" or "heterearene triyl group" refer to a heteroarylene group as defined above, wherein one hydrogen atom at any position on the heteroarylene group is replaced by another bonding site to form a trivalent group. In the case of polycyclic heteroarene triyls, their bonding sites are located either within the same ring or in different rings. Heteroarene triyls may be carbon-bonded or nitrogen-bonded, if possible. For example, pyrrole triyl, imidazole triyl, or pyrazole triyl may be N-linked or C-linked.

[0085] In the present invention, the terms "alkanetetrayl" or "alkanetetrayl group" refer, in each case, to the alkanetetrayl group as defined above, which usually has 1 to 30 carbon atoms, and which forms a tetravalent group by replacing one hydrogen atom at any position of the alkanetetrayl with an additional bonding site. Therefore, alkanetetrayl is a tetravalent, branched or unbranched, saturated aliphatic chain. Alkanetetrayl may be substituted with one or more substituents.

[0086] In this invention, the terms “dicarbonyl,” “tricarbonyl,” and “tetracarbonyl,” or “dicarbonyl group,” “tricarbonyl group,” and “tetracarbonyl group,” refer to divalent, trivalent, and tetravalent groups, respectively, that form bonds through two, three, and four carbon atoms of C(O) groups.

[0087] <Method for producing the O-iminoisourea compound of the present invention> The O-iminoisourea compound of the present invention can be produced by reacting a hydroxamate derivative, which is an intermediate, with a carbodiimide derivative (Step 3: Synthesis of the O-iminoisourea compound). The hydroxamate derivative is an intermediate for the O-iminoisourea compound of the present invention, as well as an intermediate for the O-iminoisourea compound salt and O-iminoisourea complex of the present invention.

[0088] <Method for producing hydroxysamate derivatives> A method for producing a hydroxamate derivative according to one embodiment of the present invention (also referred to as "the hydroxamate derivative production method of the present invention") can be carried out according to the following flowchart.

[0089] TIFF2026167655000012.tif55170

[0090] In other words, the compound represented by the above general formula (1) (also referred to as "oxime chloride derivative (1)") is reacted with the silylating agent represented by the above formula in the presence of a base to synthesize the oxime chloride silyl ether derivative of the above general formula (2) (also referred to as "oxime chloride silyl ether derivative (2)") (Step 1: Synthesis of oxime chloride silyl ether derivative). Next, the oxime chloride silyl ether derivative (2) is reacted with a metal alkoxide represented by the general formula (3) (also referred to as "metal alkoxide (3)") to synthesize a hydroxamate derivative represented by the general formula (4) (also referred to as "hydroxamate derivative (4)") (Step 2: Synthesis of hydroxamate derivative), which is a method for producing a hydroxamate derivative.

[0091] L1 and L2 in equation (1) are the same as L1 and L2 in equation (I) described above. The leaving group in the formula representing a silylating agent is anionic leaving group such as a halide ion or a sulfonium ion. The formulas representing the silylating agent and formula (2), R a , R b and R c Each of these is independent of C1~C 10 Alkyl alkyl groups, or C1-C 10 C6-C may be substituted with alkyl groups. 20 It is an aryl group.

[0092] A method for producing hydroxamate derivatives is disclosed, for example, in Japanese Patent No. 2543665. This method involves synthesizing an oxime chloride derivative and reacting the oxime chloride derivative with a metal alkoxide to obtain a hydroxymate derivative. When sodium methoxide, which is nucleophilic, is used as the metal alkoxide, methyl-benzohydroxamate can be obtained in 50% yield.

[0093] TIFF2026167655000013.tif37170

[0094] When the inventors followed this reaction example and used t-butyloxypotassium as the metal alkoxide, as shown in the flowchart below, only the decomposition reaction of oxime chloride proceeded, and no hydroxamate derivative was obtained at all.

[0095] TIFF2026167655000014.tif42170

[0096] In contrast, according to the hydroxamate derivative production method of the present invention, the reaction between oxime chloride silyl ether and metal alkoxide does not proceed via an unstable intermediate. Therefore, the decomposition reaction of oxime chloride does not proceed, and only the substitution reaction of the alkoxy group with the chlorine atom bonded to oxime chloride (1) proceeds with high selectivity. As a result, even if the metal alkoxide is a metal alkoxide with low reactivity such as t-butyloxypotassium, hydroxamate derivatives can be synthesized in good yield.

[0097] TIFF2026167655000015.tif52170

[0098] Regarding the synthesis of hydroxamate (4), we will describe the case where L1=R1 and L2=R2 for n=1.

[0099] TIFF2026167655000016.tif52170

[0100] (Oximo chloride derivative (1)) Oxime chloride derivatives (1) can be produced by known methods. Oxime derivatives (1) can be synthesized by synthesizing oxime derivatives from aldehyde derivatives and hydroxylamine or hydroxylamine salts, and then reacting the oxime derivatives with halogenating reagents.

[0101] One known method for synthesizing oxime derivatives is Synthesis, 50, 1640-(2018). This method involves reacting an aldehyde with hydroxylamine or a hydroxylamine salt in ethyl alcohol or a mixed solvent of ethyl alcohol and water. It is common practice to adjust the pH of the reaction solution by adding basic substances such as sodium hydroxide or sodium carbonate during the reaction. The reaction temperature is typically 60-120°C.

[0102] Oxime chloride derivatives (1) can be synthesized by the reaction of an oxime compound with a halogenating agent, such as N-chlorosuccinimide, according to conditions described, for example, in J. Org. Chem., 45, 3916-(1980). This reaction can be carried out in solvents such as toluene, tetrahydrofuran, and N,N-dimethylformamide.

[0103] (Step 1: Synthesis of oxime chloride silyl ether derivatives) In step 1, the oxime chloride derivative (1) is reacted with the silylating agent shown in the above formula in the presence of a base to synthesize the oxime chloride silyl ether derivative (2).

[0104] Various organic and inorganic bases can be used as the base in step 1. Examples of the aforementioned organic bases include triethylamine, diisopropylethylamine, pyridine, 2,6-lutidine, and diazacyclo[5,4,0]-7-undecene. However, the selection is not limited to these. Examples of the inorganic bases mentioned above include sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate. However, the list is not limited to these. Among these, from the viewpoint of reactivity and ease of purification, organic bases such as triethylamine, diisopropylethylamine, and diazabicyclo[5,4,0]-7-undecene are preferred, and triethylamine is particularly preferred.

[0105] The leaving group in the formula for a silylation agent is an anionic leaving group, such as halide ions like chlorine, bromine, and iodine, or sulfonic acid anions like azido anions, cyano anions, and trifluolomethanesulfonic acid anions. In addition, when the leaving group is an amine such as dimethylamino, diethylamino, or 1-imidazolyl, or an amide compound such as trifluoromethylacetamide, their conjugate base becomes the leaving group. In the formula representing the silylating agent, R a , R b and R c Each of these is independent of C1~C 10 Alkyl alkyl groups, or C1-C 10 C6-C may be substituted with alkyl groups. 20 It is an aryl group.

[0106] Examples of silylating agents that can be used include silyl halides such as silyl chloride, silyl bromide, and silyl iodide, silyl azide, silyl cyanide, silyl polyfluoroalkyl sulfonic acid esters, silylamines, silyl imidazoles, N-silylamides, and silylamides such as N,O-bissilylamides. Furthermore, substituents R bonded to silicon a , R b , R c Each of these can independently be a methyl group, an ethyl group, an isopropyl group, a phenyl group, a substituted phenyl group, or the like.

[0107] Specific silylation agents include, for example, trimethylsilyl chloride, triethylsilyl chloride, butyldimethylsilyl chloride, butyldiphenylsilyl chloride, triphenylsilyl chloride, trimethylsilyl bromide, triethylsilyl bromide, trimethylsilyl iodide, trimethylsilyl azide, trimethylsilyl cyanide, trimethylsilyl trifluoromethylsulfonate, butyldimethylsilyl trifluoromethylsulfonate, trimethylsilyldimethylamine, trimethylsilyldiethylamine, trimethylsilyl imidazole, triethylsilyl imidazole, N,O-bis(trimethylsilyl)acetamide, and N,O-bis(trimethylsilyl)trifluoroacetamide. Among these, butyldimethylsilyl chloride is particularly preferred due to its high reactivity with the silylating agent and the stability of the resulting oximesilyl ether. The various silylating agents mentioned above are commercially available.

[0108] In step 1, it is preferable to add a solvent as needed. As the solvent, any common solvent can be used, except for protic solvents that react with the silylating agent. Specifically, examples include hydrocarbons such as hexane, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; ethers such as tetrahydrofuran and butyl methyl ether; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; and dimethyl sulfoxides. In particular, from the viewpoint of the solubility of the reaction raw material oxime and silylating agent, amides, dimethyl sulfoxides, and esters are preferred, and N,N-dimethylformamide is especially preferred.

[0109] The reaction temperature in step 1 is preferably controlled so that the liquid temperature of the reaction mixture is between -78°C and 100°C, and more preferably between -30°C and 80°C, and more preferably between -10°C and 50°C.

[0110] (Step 2: Synthesis of hydroxamate derivatives) In step 2, the oxime chloride silyl ether derivative (2) is reacted with a metal alkoxide (3) to synthesize a hydroxamate derivative (4). The synthesis procedure in Step 2 is the same as the reaction procedure between oxime chloride and metal alkoxide disclosed in Japanese Patent No. 2543665.

[0111] The metal alkoxide (3) can be a commercially available reagent or can be prepared by known methods. Specifically, commercially available solid alkoxides, such as sodium methoxide or potassium butyloxyhydrate, can be used in their dissolved or suspended form in a solvent. Alternatively, a methanol solution of commercially available sodium methoxide can be used. Furthermore, metal alkoxides prepared by the reaction of alcohol with elemental sodium or sodium hydride can also be used. However, the method is not limited to these.

[0112] Any reaction solvent that does not react with the reaction starting materials, metal alkoxide (3) and oxime chloride silyl ether (2), can be used. Specifically, examples include hexane, toluene, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. In particular, N,N-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran are preferred from the viewpoint of solubility of the reaction raw materials, with N,N-dimethylformamide being especially preferred. Furthermore, since alkoxides are deactivated by water, solvents with low water content are preferred.

[0113] In step 2, the reaction temperature is preferably controlled so that the liquid temperature of the reaction mixture is between -78°C and 100°C, and more preferably between -30°C and 80°C, and more preferably between -10°C and 50°C.

[0114] Even when n > 2, a hydroxamate derivative having a linker structure can be obtained by the same reaction as in steps 1 and 2.

[0115] (Step 3: Synthesis of an O-iminoisourea compound where n=1 and L3 is hydrogen) In step 3, as shown in the following flow chart, the hydroxamate derivative (4) is reacted with the carbodiimide derivative represented by the following general formula (5) (also referred to as "carbodiimide derivative (5)") to synthesize the O-iminoisourea compound represented by formula (I). However, the O-iminoisourea compound synthesized in step 3 is an O-iminoisourea compound in which n=1 in general formula (I) and L3 is hydrogen.

[0116] The procedure for the addition reaction in step 3 is similar to the procedure described in, for example, Japanese Patent No. 5693565. However, it is not limited to this method.

[0117] TIFF2026167655000017.tif42170

[0118] The carbodiimide derivative (5) can be a commercially available compound. Examples include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, N,N'-bis(O-tolyl)carbodiimide, N,N'-bis(p-tolyl)carbodiimide, and N,N'-bis(trimethylsilyl)carbodiimide.

[0119] In Step 3, various solvents can be used as needed. Examples include tetrahydrofuran, hexane, toluene, acetonitrile, N,N-dimethylformamide, dichloromethane, chloroform and the like.

[0120] The reaction temperature of Step 3 is preferably controlled such that the liquid temperature of the reaction mixture is from -78°C to 100°C, more preferably controlled to be from -30°C to 80°C, and even more preferably controlled to be from -10°C to 60°C.

[0121] In the reaction of Step 3, a catalyst can be used to promote the reaction. Examples of the catalyst may include basic compounds, Brønsted acids, Lewis acids and the like. Examples of the basic compound may include alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, and amine compounds such as triethylamine, diazabicyclo[5.4.0]-7-undecene and the like. Examples of the Brønsted acid may include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like. Examples of the Lewis acid may include boron trifluoride, zinc chloride and the like.

[0122] <Method for producing O-iminoisourea compound wherein n=1 and L3 is other than hydrogen> The O-iminoisourea compound in which n=1 in the general formula (I) and L3 is other than hydrogen can be synthesized from the O-iminoisourea with n=1 and L3 being hydrogen obtained in Step 3 and a reactant having the structure of L3 to be introduced.

[0123] TIFF2026167655000018.tif47170

[0124] For example, if L3 is an alkyl group, an O-iminoisourea with n=1 and L3 being hydrogen can be reacted with an alkyl compound having a leaving group, such as an alkyl bromide, alkyl iodide, or alkyl sulfonic acid ester, which is a derivative of L3 to be introduced, to obtain an O-iminoisourea(I) with n=1 and L3 being an alkyl group.

[0125] Furthermore, when L3 is a C(O) alkyl group, an O-iminoisourea compound with n=1 and L3 being hydrogen can be obtained by reacting it with an alkylacyl compound such as an alkyl C(O) chloride, alkyl C(O) bromide, or alkyl carboxylic acid anhydride.

[0126] In the reaction between O-iminoisourea compounds and L3, additives can be used to accelerate the reaction. The additives used in this case are basic compounds, such as alkali metal hydroxides, alkali metal hydrides, triethylamines, and amine compounds such as diazabicyclo[5,4,0]-7-undecene.

[0127] Various solvents can be used in the above reaction. Examples include tetrahydrofuran, hexane, toluene, acetonitrile, chloroform, dichloromethane, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, and N-methylpiperidine.

[0128] O-iminoisourea compounds in general formula (I) where n=2, L1 is a linker, and L3 is hydrogen can be synthesized by the reaction of a hydroxyamate (6) with L1 as a linker and a carbodiimide derivative (5), as shown in the following flowchart.

[0129] TIFF2026167655000019.tif49170

[0130] O-iminoisourea compounds in general formula (I) where n=2, L2 is the linker, and L3 is hydrogen can be synthesized by the reaction of a hydroxamate (7) with L2 as the linker and a carbodiimide derivative (5), as shown in the following flowchart.

[0131] TIFF2026167655000020.tif48170

[0132] In general formula (I), an O-iminoisourea compound with n=2 and L3 as a linker can be obtained from an O-iminoisourea with n=1 and L3 as hydrogen synthesized in step 3, and a reagent having the structure of a divalent linker L3, as shown in the following flow chart.

[0133] TIFF2026167655000021.tif88170

[0134] By using trivalent and tetravalent substituents for L1, L2, and L3, O-iminoisourea compounds with n=3 and n=4 substituents can be obtained, respectively.

[0135] <Method for producing O-iminoisourea compound salts of the present invention> The O-iminoisourea compound salt of the present invention is, as shown in the following flowchart, an O-iminoisourea compound of the present invention, i.e., an O-iminoisourea compound represented by the above general formula (I) (also referred to as "O-iminoisourea compound (I)"), and an acidic compound or C1-C represented by the following formula. 10 It can be produced by reacting alkyl halides (collectively referred to as "YX") with an O-iminoisourea compound salt represented by the above general formula (II) (also referred to as "O-iminoisourea compound salt (II)"), i.e., by a salt formation reaction. However, the method is not limited to this.

[0136] TIFF2026167655000022.tif55170

[0137] By mixing O-iminoisourea compound (I) with YX, an O-iminoisourea compound salt (II) can be obtained.

[0138] Examples of acidic compounds represented by YX include monocarboxylic acids such as formic acid, acetic acid, and benzoic acid; monosulfonic acids such as methanesulfonic acid and toluenesulfonic acid; dicarboxylic acids such as glutaric acid, succinic acid, phthalic acid, and terephthalic acid; disulfonic acids such as 1,2-benzenedisulfonic acid and 1,4-benzenedisulfonic acid; and inorganic acids. Examples of such inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, bisulfate, and tetrafluoroboric acid.

[0139] C1~C, represented by YX 10 Examples of alkyl halogenated compounds include methyl iodide, ethyl iodide, butyl iodide, hexyl iodide, 2-ethylhexyl iodide, decyl iodide, methyl bromide, butyl bromide, hexyl bromide, 2-ethylhexyl bromide, and decyl bromide.

[0140] Examples of reaction solvents that can be used in the synthesis of the O-iminoisourea compound salt of the present invention include hexane, toluene, tetrahydrofuran, dioxane, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide.

[0141] The reaction temperature is preferably controlled so that the liquid temperature of the reaction mixture in the chamber is between -78°C and 100°C, and more preferably between -30°C and 80°C, and more preferably between -10°C and 50°C.

[0142] <Method for producing the O-iminoisourea complex of the present invention> The O-iminoisourea complex of the present invention can be produced by reacting the O-iminoisourea compound of the present invention, i.e., the O-iminoisourea compound represented by the above general formula (I) (also referred to as "O-iminoisourea compound (I)") with a Lewis acid compound represented by the following formula (also referred to as "pZ"), i.e., by a complex formation reaction, to produce the O-iminoisourea complex represented by the above general formula (III) (also referred to as "O-iminoisourea complex (III)"). However, the method of production is not limited to this method.

[0143] TIFF2026167655000023.tif52170

[0144] Lewis acid compounds denoted by pZ include, for example, boron halides, aluminum halides, C1-C4 alkyl oxyboric acids, and C6-C2 alkyl oxyboric acids. 10 Examples include aryl oxyboric acid, zinc chloride (2), copper chloride (1), etc. p is an integer less than or equal to n.

[0145] Examples of reaction solvents that can be used in the synthesis of the O-iminoisourea complex of the present invention include hexane, toluene, tetrahydrofuran, dioxane, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide.

[0146] The reaction temperature is preferably controlled so that the liquid temperature of the reaction mixture in the chamber is between -78°C and 100°C, and more preferably between -30°C and 80°C, and more preferably between -10°C and 50°C.

[0147] <Use as a thermal polymerization initiator> Any one or more of the O-iminoisourea compounds represented by general formula (I), the O-iminoisourea compound salts represented by general formula (II), and the O-iminoisourea complexes represented by general formula (III) can be suitably used as thermal polymerization initiators. In this context, the O-iminoisourea compound represented by the general formula (I) includes the O-iminoisourea compounds described in the aforementioned Non-Patent Document 6: Journal de la Societe Chimique de Tunisie (1986), 2(3), 9-13. Furthermore, a thermal polymerization initiator consisting of one or more of the O-iminoisourea compounds represented by general formula (I), the O-iminoisourea compound salts represented by general formula (II), and the O-iminoisourea complexes represented by general formula (III), is also referred to as the "thermal polymerization initiator of the present invention."

[0148] Iminoisourea compounds and their salts or complexes are stable at room temperature and, as shown in the formula below, generate radicals upon heating, exhibiting polymerization activity; therefore, they are known to function as thermal polymerization initiators. However, among the generated radicals, the O radical on the isourea side has polymerization activity, while the N radical on the other side is polymerization inactive, resulting in a small number of initiating radicals and a problem with reactivity.

[0149] TIFF2026167655000024.tif51170

[0150] In the case of the O-iminoisourea compound, the O-iminoisourea compound salt, or the O-iminoisourea complex of the present invention, for example, when L1 is a t-butyl group, sequential decomposition occurs to generate Me radicals as follows. In this case, sequential decomposition converts polymerization-inactive species, such as the N radical mentioned above, into polymerization-active species, thereby increasing reactivity. Furthermore, while radicals are generally stabilized by bonded substituents, this stabilization can sometimes lead to a decrease in reactivity. Since Me radicals lack substituents, they are not stabilized and exhibit high reactivity in radical reactions. Furthermore, because Me radicals lack substituents, they are sterically small and exhibit high reactivity compared to larger radicals with substituents, as they are more favorably positioned to move to the reaction site and associate with highly polymerizable compounds that can easily become crowded.

[0151] TIFF2026167655000025.tif47170

[0152] An example of an L1 substituent that can decompose sequentially to generate an Me radical is the 2-phenyl-2-propyl group. According to Polyer. J., Vol. 29, No. 4 (1997), it has been shown that the 2-phenyl-2-propyl radical generates an Me radical through sequential decomposition. When this substituent is introduced into O-iminoisourea, the sequential decomposition shown in the following equation is thought to proceed.

[0153] TIFF2026167655000026.tif53170

[0154] Furthermore, the generation of a Me radical has been reported with respect to the 2-methyl-3-butenyl group in JOC, 63, 8366-8372, 1998. When this substituent is introduced into O-iminoisourea, the following reaction is thought to proceed.

[0155] TIFF2026167655000027.tif45170

[0156] Based on the results of the present invention and literature reports, it is expected that the following O-iminoisourea compounds having a 2-methyl-2-butyl group, a 3-methyl-3-pentyl group, and a 1,1-diphenylethyl group will also generate Me radicals.

[0157] TIFF2026167655000028.tif44170

[0158] Furthermore, if an acetyl group is introduced at L1, sequential cleavage from the N radical can be expected to generate a Me radical accompanied by the generation of carbon dioxide.

[0159] TIFF2026167655000029.tif41170

[0160] Considering the mechanism of action described above, it can be inferred that the substituents L2-L3, R4, and R5, other than L1, can have any structure that produces the same effect. The following compounds are examples of specific compounds that can achieve the effects described above. However, the list is not limited to these.

[0161] TIFF2026167655000030.tif79170

[0162] Furthermore, the mechanism of action described above can also be applied to the generation structure of other types of radicals. When R1 is a group other than a butyl group, for example, a MeO group will generate a MeO radical, and a PhO group will generate a PhO radical, which can be expected to exert a similar effect to the Me radical. In this case as well, considering the mechanism of action, it is presumed that substituents L2-L3, R4, and R5 other than L1 will exert a similar effect regardless of their structure. The following compounds are examples of specific examples that are thought to exert such effects, but are not limited to these.

[0163] TIFF2026167655000031.tif46170

[0164] The above description of the thermal polymerization initiator pertains to the O-iminoisourea compound of the present invention, but the same applies to its salts or complexes. Therefore, the O-iminoisourea compound of the present invention in the above description can be read as its salt or complex.

[0165] <<Polymerizable Composition of the Invention>> A polymerizable composition according to an example of an embodiment of the present invention (referred to as "the polymerizable composition of the present invention") is a composition comprising (A) a polymerizable compound, and optionally, other components such as (C) an alkali-soluble resin, (D) a photopolymerization initiator, (E) a colorant, (F) a chain transfer agent, etc. In this context, the O-iminoisourea compound represented by the general formula (I) includes the O-iminoisourea compounds described in the aforementioned Non-Patent Document 6: Journal de la Societe Chimique de Tunisie (1986), 2(3), 9-13.

[0166] <(A) Thermal polymerization initiator of the present invention> (A) The thermal polymerization initiator of the present invention may be any one of the following: an O-iminoisourea compound represented by general formula (I), an O-iminoisourea compound salt represented by general formula (II), and an O-iminoisourea complex represented by general formula (III), or a mixture of two or more of these. In this context, the O-iminoisourea compound represented by the general formula (I) includes the O-iminoisourea compounds described in the aforementioned Non-Patent Document 6: Journal de la Societe Chimique de Tunisie (1986), 2(3), 9-13.

[0167] The content of (A) the thermal polymerization initiator of the present invention in the polymerizable composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.2% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total solid content of the polymerizable composition. The upper and lower limits can be arbitrarily combined, for example, 0.01 to 25% by mass is preferred, 0.05 to 15% by mass is more preferred, and 0.2 to 10% by mass is even more preferred. Setting the value above the lower limit tends to improve curability. Setting the value below the upper limit tends to improve composition stability. (A) The thermal polymerization initiator of the present invention may be used alone or in combination of two or more types.

[0168] <(B) Polymerizable compound> The polymerizable composition of the present invention contains (B) a polymerizable compound. It is believed that the inclusion of (B) the polymerizable compound results in high sensitivity. The polymerizable compound (B) used here refers to a compound having one or more ethylenically unsaturated bonds (ethylenically double bonds) in its molecule. However, from the viewpoint of polymerizability and crosslinking properties, it is preferable that the compound has two or more ethylenically unsaturated bonds in its molecule. Furthermore, it is even more preferable that the unsaturated bonds are derived from a (meth)acryloyloxy group, that is, that the compound is a (meth)acrylate compound.

[0169] In the polymerizable composition of the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule as the polymerizable compound (B). The number of ethylenically unsaturated groups in a polyfunctional ethylenically monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. It is also preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, and particularly preferably 7 or less. The upper and lower limits can be combined arbitrarily; for example, 2 to 15 is preferred, 3 to 10 is more preferred, 4 to 8 is even more preferred, and 5 to 7 is particularly preferred. Setting the value above the lower limit tends to improve polymerizability and result in higher sensitivity. Setting the value below the upper limit tends to result in better developability.

[0170] (B) Examples of polymerizable compounds include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

[0171] Examples of esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids include acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters obtained by replacing the acrylate of these compounds with methacrylate; itaconic acid esters obtained by replacing the acrylate of these compounds with itaconate; crotonic acid esters obtained by replacing the acrylate of these compounds with cronate; and maleic acid esters obtained by replacing the acrylate of these compounds with maleate.

[0172] Examples of esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. Esters obtained by the esterification reaction of polyhydroxy compounds, such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single compounds, but examples include condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

[0173] Other examples of polymerizable compounds (B) used in the polymerizable composition of the present invention include, for example, urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as addition products of a polyvalent epoxy compound with a hydroxyl group-containing (meth)acrylic acid ester or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. Examples of urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoei Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Among these, from the viewpoint of sensitivity, it is preferable to use ester (meth)acrylates or urethane (meth)acrylates as the polymerizable compound (B), and it is more preferable to use dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-tris(meth)acryloyloxymethylethyl phthalic acid, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate, or dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate. These may be used individually or in combination of two or more types.

[0174] In the polymerizable composition of the present invention, the weight-average molecular weight of the polymerizable compound (B) is not particularly limited, but from the viewpoint of curability and taper angle, it is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and also preferably 1000 or less, more preferably 700 or less. The upper and lower limits can be arbitrarily combined, for example, 100 to 1000 is preferred, 150 to 1000 is more preferred, 200 to 1000 is even more preferred, 300 to 700 is even more preferred, 400 to 700 is particularly preferred, and 500 to 700 is most preferred.

[0175] (B) The number of carbon atoms in the polymerizable compound is not particularly limited, but from the viewpoint of curability and taper angle, it is preferably 7 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, particularly preferably 25 or more, and also preferably 50 or less, more preferably 40 or less, even more preferably 35 or less, particularly preferably 30 or less. The upper and lower limits can be arbitrarily combined, for example, 7 to 50 is preferred, 10 to 50 is more preferred, 15 to 40 is even more preferred, 20 to 35 is even more preferred, and 25 to 30 is particularly preferred.

[0176] The content of the polymerizable compound (B) in the polymerizable composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and also preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less. The upper and lower limits can be arbitrarily combined, for example, 5 to 80% by mass is preferred, 10 to 70% by mass is more preferred, 20 to 60% by mass is even more preferred, 30 to 55% by mass is even more preferred, and 40 to 50% by mass is particularly preferred. Setting the value above the lower limit tends to result in appropriate internal curing properties. Setting the value below the upper limit tends to result in good developability.

[0177] <(C) Alkali-soluble resin> The polymerizable composition of the present invention may contain (C) an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it is a resin that can be developed with an alkaline developer. Examples of alkali-soluble resins include various resins containing carboxyl groups and / or hydroxyl groups. Among these, resins having carboxyl groups are preferred.

[0178] [(c) Alkali-soluble resin having an ethylenic double bond] In the polymerizable composition of the present invention, it is preferable that the (C) alkali-soluble resin includes (c) an alkali-soluble resin having an ethylenically double bond (hereinafter sometimes abbreviated as "(c) alkali-soluble resin"). Including (c) an alkali-soluble resin having an ethylenically double bond tends to increase sensitivity. (c) The specific structure of the alkali-soluble resin having an ethylenic double bond is not particularly limited, but from the viewpoint of developability, (c1) epoxy (meth)acrylate resin and / or (c2) acrylic copolymer resin are preferred, and from the viewpoint of tapered shape, (c1) epoxy (meth)acrylate resin is more preferred.

[0179] (C) When the alkali-soluble resin contains (c1) epoxy (meth)acrylate resin, the content of (c1) epoxy (meth)acrylate resin in (C) alkali-soluble resin is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass or less. The upper and lower limits can be arbitrarily combined. For example, 30 to 100% by mass is preferred, 50 to 100% by mass is more preferred, 70 to 100% by mass is even more preferred, 80 to 100% by mass is even more preferred, and 90 to 100% by mass is particularly preferred. Setting the value above the lower limit tends to improve the tapered shape.

[0180] The acid or ester compound having an ethylenically unsaturated bond can be used in an amount that is preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents, per 1 chemical equivalent of the epoxy group of the epoxy resin. The temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C. The polybasic acid (anhydride) can be used in an amount that is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of the hydroxyl group produced in the addition reaction.

[0181] When the polymerizable composition of the present invention contains (c1) epoxy (meth)acrylate resin, the content of (c1) epoxy (meth)acrylate resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and also preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, particularly preferably 50% by mass or less. The upper and lower limits can be arbitrarily combined, for example, 5 to 90% by mass is preferred, 10 to 90% by mass is more preferred, 20 to 70% by mass is even more preferred, 30 to 60% by mass is even more preferred, and 40 to 50% by mass is particularly preferred. Setting the value above the lower limit tends to improve developability. Also, setting the value below the upper limit tends to improve curability.

[0182] Furthermore, when the polymerizable composition of the present invention contains (c2) acrylic copolymer resin, the content of (c2) acrylic copolymer resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and also preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, in the total solid content of the polymerizable composition. The upper and lower limits can be arbitrarily combined, for example, 5 to 90% by mass is preferred, 10 to 90% by mass is more preferred, 20 to 80% by mass is even more preferred, and 30 to 70% by mass is even more preferred. Setting the value above the lower limit tends to improve developability. Also, setting the value below the upper limit tends to result in a good tapered shape.

[0183] Furthermore, the total content of (C) alkali-soluble resin and (B) polymerizable compound in the total solid content of the polymerizable composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, even more particularly preferably 80% by mass or more, most preferably 90% by mass or more, and also preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. The upper and lower limits can be arbitrarily combined, for example, 5 to 99% by mass is preferred, 10 to 99% by mass is more preferred, 30 to 99% by mass is even more preferred, 50 to 97% by mass is even more preferred, 70 to 97% by mass is particularly preferred, 80 to 95% by mass is particularly preferred, and 90 to 95% by mass is most preferred.

[0184] Setting the value above the lower limit tends to improve developability. Conversely, setting it below the upper limit allows for an increase in the amount of thermal polymerization initiator, which tends to improve curability. The blending ratio of (C) alkali-soluble resin to (B) polymerizable compound in the polymerizable composition is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, and also preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less, with the upper and lower limits being any combination; for example, 50 to 400 parts by mass is preferred, and 60 to 300 parts by mass is more preferred. Setting the ratio above the lower limit tends to improve developability. Setting the ratio below the upper limit tends to improve curability.

[0185] <(D) Photopolymerization initiator> The polymerizable composition of the present invention may further contain (D) a photopolymerization initiator. (D) The photopolymerization initiator is a component that directly absorbs light, causes a decomposition reaction or hydrogen abstraction reaction, and generates polymerization-active radicals, thereby polymerizing (B) the polymerizable compound. For example, it is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated bonds of (B) the polymerizable compound.

[0186] The polymerizable composition of the present invention may use (D) a photopolymerization initiator, which may be a photopolymerization initiator commonly used in this field. Examples of such photopolymerization initiators include metallocene compounds containing titanocene compounds as described in Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197; hexaarylbiimidazole derivatives as described in Japanese Patent Publication No. 2000-56118; radical activators such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives as described in Japanese Patent Publication No. 10-39503; and oxime ester compounds as described in Japanese Patent Publication No. 2000-80068 and Japanese Patent Publication No. 2006-36750. Specifically, examples of metallocene compounds include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl), and dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl). Examples include rutitanium di(2,6-difluorophenyl), dicyclopentadienyltitanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), and dicyclopentadienyltitanium [2,6-di-fluoro-3-(pyro-1-yl)-phenyl]. Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0187] The photopolymerization initiator may, if necessary, be formulated with sensitizing dyes and polymerization accelerators corresponding to the wavelength of the image exposure light source to enhance sensitivity.

[0188] <(E) Colorants> The polymerizable composition of the present invention may contain (E) a coloring agent for the purpose of coloring the composition. (E) As the coloring agent, known coloring agents such as pigments and dyes can be used.

[0189] <(F) Chain transfer agent> The polymerizable composition of the present invention may contain a (F) chain transfer agent. Including a (F) chain transfer agent improves radical deactivation due to oxygen inhibition near the surface, thereby enhancing surface hardening properties and tending to increase the taper angle. (F) Examples of chain transfer agents include mercapto group-containing compounds and carbon tetrachloride, with mercapto group-containing compounds being more preferred due to their tendency to exhibit a high chain transfer effect. Mercapto group-containing compounds tend to enhance surface hardening because their SH bond energy is low, which facilitates bond cleavage and chain transfer reactions.

[0190] <Coating properties improver, developer improver> The polymerizable composition of the present invention may contain a coatability enhancer or a developer enhancer to improve coatability and developer solubility. For example, known surfactants can be used as coating improvers or developer improvers.

[0191] <UV absorber> The polymerizable composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing specific wavelengths of the light source used for exposure. Including an ultraviolet absorber tends to yield effects such as improving the tapered angle shape after development and reducing the residue remaining in the unexposed areas after development. As an ultraviolet absorber, from the viewpoint of inhibiting light absorption by photopolymerization initiators, for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used.

[0192] Examples of ultraviolet absorbers include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes. These UV absorbers may be used individually or in combination of two or more types.

[0193] <Polymerization inhibitor> The polymerizable composition of the present invention may contain a polymerization inhibitor. It is believed that the inclusion of a polymerization inhibitor inhibits radical polymerization, thereby increasing the taper angle of the resulting septum.

[0194] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, methylhydroquinone and methoxyphenol are preferred from the viewpoint of polymerization inhibitory ability, and methylhydroquinone is more preferred. Polymerization inhibitors may be used individually or in combination of two or more. Typically, when (B) alkali-soluble resins are manufactured, polymerization inhibitors may be present in the resin, and these may be used as polymerization inhibitors in the polymerizable composition of the present invention. Alternatively, in addition to the polymerization inhibitors present in the resin, the same or different polymerization inhibitors may be added during the manufacture of the polymerizable composition.

[0195] <Silane coupling agent> The polymerizable composition of the present invention may contain a silane coupling agent to improve adhesion to the substrate. Examples of silane coupling agents that can be used include epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred. When the polymerizable composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 20% by mass or less, and more preferably 15% by mass or less, of the total solid content of the polymerizable composition, from the viewpoint of adhesion.

[0196] <Phosphate-based adhesion enhancer> The polymerizable composition of the present invention may contain a phosphate-based adhesion enhancer to improve adhesion to the substrate. As the phosphoric acid-based adhesion enhancer, (meth)acryloyloxy group-containing phosphates are preferred, and for example, phosphoric acid-based adhesion enhancers described in Japanese Patent Publication No. 2025-181849 and Japanese Patent Publication No. 2022-108724 can be used.

[0197] When the polymerizable composition of the present invention contains a phosphoric acid-based adhesion improver, the content thereof is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, still more preferably 0.3 mass% or more in the total solid content of the polymerizable composition, and is preferably 5 mass% or less, more preferably 3 mass% or less, still more preferably 1 mass% or less. The above upper and lower limits can be arbitrarily combined, for example, preferably 0.1 to 5 mass%, more preferably 0.2 to 3 mass%, and still more preferably 0.3 to 1 mass%. When the content is not less than the above lower limit, the adhesion to the substrate tends to be improved. In addition, when the content is not more than the above upper limit, the surface curability tends to be improved.

[0198] <Solvent> The polymerizable composition of the present invention usually contains a solvent, and is used in a state where the aforementioned components are dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the organic solvents described below.

[0199] Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, etc.; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, di Glycol dialkyl ethers such as ethylene glycol dibutyl ether and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and 3-methoxy-1-butyl acetate;Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, di Ketones such as butyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, and methoxymethylpentanone; monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; n-pentane Aliphatic hydrocarbons such as n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, and isobutyrate. Chain-like or cyclic esters such as ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone;Nitriles such as acetonitrile and benzonitrile; and tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

[0200] Examples of commercially available solvents corresponding to the above include mineral spirits, Varsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all are trade names). The solvent can dissolve or disperse each component in the polymerizable composition, and is selected according to the method of using the polymerizable composition of the present invention. From the viewpoint of coatability, those having a boiling point of 60 to 280°C under atmospheric pressure (1013.25 hPa) are preferred, and those having a boiling point of 70 to 260°C are more preferred. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred. The solvent may be used singly or in combination of two or more kinds.

[0201] The solvent is preferably used such that the total solid content in the polymerizable composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 18% by mass or more, and is preferably 90% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less. The above upper and lower limits can be arbitrarily combined, for example, 10 to 90% by mass is preferred, 10 to 50% by mass is more preferred, 15 to 40% by mass is still more preferred, and 18 to 30% by mass is particularly preferred. By setting the content to be equal to or higher than the lower limit, a coating film tends to be obtained even for a high film thickness. In addition, by setting the content to be equal to or lower than the upper limit, appropriate coating uniformity tends to be obtained.

[0202] <Method for Preparing Polymerizable Composition of the Present Invention> The polymerizable composition of the present invention can be prepared by mixing the above components in a stirrer. The prepared polymerizable composition may be filtered using a membrane filter or the like to ensure uniformity.

[0203] <<Cured product of the present invention>> A cured product according to one embodiment of the present invention (referred to as "cured product of the present invention") is a cured product of the polymerizable composition of the present invention. The polymerizable composition of the present invention can be obtained by heating and curing it.

[0204] Next, a method for producing a cured product using the polymerizable composition of the present invention will be described. The cured product of the present invention can be produced using one or more of the following as a thermal polymerization initiator: an O-iminoisourea compound represented by general formula (I), an O-iminoisourea compound salt represented by general formula (II), and an O-iminoisourea complex represented by general formula (III). In this context, the O-iminoisourea compound represented by the general formula (I) includes the O-iminoisourea compounds described in the aforementioned Non-Patent Document 6: Journal de la Societe Chimique de Tunisie (1986), 2(3), 9-13.

[0205] Specifically, it is preferable to form a cured product by performing the following steps (1) to (4). Step (1): A step of forming a coating film of a polymerizable composition on a substrate. Step (2): A step of exposing at least a portion of the coating film formed in step (1). Step (3): A step to develop the coating film exposed in step (2). Step (4): A step in which the coating developed in step (3) is fired.

[0206] <Step (1): Step of forming a coating film of polymerizable composition on a substrate> [substrate] The substrate used to form the cured product of the present invention is not particularly limited in material, as long as it has adequate strength. Transparent substrates are mainly used, but examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic resins, and various types of glass. Among these, glass and heat-resistant resins are preferred from the viewpoint of heat resistance. In addition, transparent electrodes such as ITO and IZO may be deposited on the surface of the substrate. Besides transparent substrates, it is also possible to form it on TFT arrays or touch panels. For example, it is suitably used in panel structures such as those described in Japanese Patent Application Publication No. 2021-110936. To improve surface properties such as adhesion, the substrate may be subjected to treatments as needed, such as corona discharge treatment, ozone treatment, or thin-film formation of various resins, including silane coupling agents and urethane resins. The thickness of the substrate is typically in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. Furthermore, when performing thin film formation treatment on various resins, the film thickness is typically in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

[0207] [Method for supplying polymerizable composition to a substrate] The polymerizable composition of the present invention is typically supplied onto a substrate in a dissolved or dispersed state in a solvent. This can be done by conventionally known methods, such as the spinner method, wire bar method, flow coating method, die coating method, roll coating method, or spray coating method. Alternatively, it may be supplied in a patterned form by methods such as inkjet or printing. Among these, the die coating method is preferable from an overall viewpoint because it significantly reduces the amount of composition used, completely eliminates the influence of mist and other contaminants that can occur with the spin coating method, and suppresses the generation of foreign matter. The amount applied varies depending on the application, but the film thickness after drying is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. It is important that the dried film thickness or the final cured film thickness is uniform across the entire substrate. If the variation is small, uneven defects that occur in the cured product can be suppressed. When using the polymerizable composition of the present invention to form cured products with different film thicknesses in a single batch, as described later, the final film thicknesses of the formed cured products will differ.

[0208] [Drying method] After supplying the polymerizable composition onto the substrate, drying is preferably performed to form a coating film. Drying is preferably done using a hot plate, IR oven, or convection oven. A vacuum drying method, in which drying is performed in a reduced-pressure chamber without raising the temperature, may also be used. Drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. Drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40°C to 100°C, and preferably in the range of 30 seconds to 3 minutes at a temperature of 50°C to 80°C, etc., depending on the type of solvent component, the performance of the dryer used, etc. Furthermore, it is preferable to carry out the process within a range that does not exceed the firing temperature described later.

[0209] <Step (2): A step of exposing at least a portion of the coating film formed in Step (1)> [Exposure method] Exposure is performed by superimposing a negative mask pattern onto the polymerizable composition coating and irradiating it with ultraviolet or visible light through this mask pattern. When using an exposure mask, the exposure mask may be placed close to the polymerizable composition coating, or the exposure mask may be placed at a distance from the coating and the exposure light projected through the mask. A scanning exposure method using laser light without a mask pattern may also be used. If necessary, to prevent a decrease in the sensitivity of the coating due to oxygen, the exposure may be performed in an oxygen-free atmosphere, or an oxygen-blocking layer such as a polyvinyl alcohol layer may be formed on the polymerizable composition coating before exposure.

[0210] When simultaneously forming cured materials with different film thicknesses, for example, an exposure mask is used that includes a light-shielding section (0% light transmittance) and multiple openings, with the opening having the highest average light transmittance (fully transparent opening) and openings with lower average light transmittance (intermediately transparent opening). This method creates a difference in the residual film percentage due to the difference in average light transmittance between the intermediately transparent opening and the fully transparent opening, i.e., the difference in exposure amount. Intermediate transmission openings can be created, for example, by a matrix-like light-shielding pattern having minute polygonal light-shielding units. Alternatively, they can be created by controlling the light transmittance using films of absorbers such as chromium-based, molybdenum-based, tungsten-based, or silicon-based materials.

[0211] The light source used for the above exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, as well as laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When using light of a specific wavelength, optical filters can also be used. The optical filter may be a thin film type in which the light transmittance at the exposure wavelength can be controlled. Examples of materials for such a filter include Cr compounds (oxides, nitrides, oxynitrides, fluorides, etc. of Cr), MoSi, Si, W, and Al. The exposure dose is typically 1 mJ / cm². 2 Preferably 5 mJ / cm² 2 More preferably 10 mJ / cm² 2 The above is true, and preferably 300 mJ / cm². 2 More preferably 200 mJ / cm² 2 More preferably, 150 mJ / cm² 2 The following applies: In the case of a proximity exposure method, the distance between the exposure target and the mask pattern is preferably 10 μm or more, more preferably 50 μm or more, further preferably 75 μm or more, and also preferably 500 μm or less, more preferably 400 μm or less, further preferably 300 μm or less.

[0212] <Step (3): Step of developing the coating film exposed in step (2)> [Development Method] After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of an alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer agent, a complexing agent, a dye or a pigment.

[0213] Examples of the alkaline compound include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic alkaline compounds such as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be a mixture of two or more kinds.

[0214] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate ester salts; and amphoteric surfactants such as alkyl betaines and amino acids.

[0215] Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Furthermore, the organic solvents may be used alone or in combination with water or aqueous solutions of alkaline compounds. There are no particular restrictions on the development conditions, but typically the development temperature is 10-50°C, preferably 15-45°C, and more preferably 20-40°C. The development method can be, for example, immersion development, spray development, brush development, or ultrasonic development. If necessary, the substrate after the development process may be subjected to additional exposure using a method similar to the exposure method described above.

[0216] <Step (4): A step to bake the coating developed in step (3)> [Firing method] The resulting coating film is preferably subjected to firing. The baking method is not particularly limited, but a hot plate, IR oven, or convection oven is preferably used. The baking temperature is preferably 50°C or higher, more preferably 70°C or higher. It is also preferably 150°C or lower, more preferably 100°C or lower, even more preferably 90°C or lower, and even more preferably 80°C or lower. The baking time is preferably 5 to 60 minutes.

[0217] [Black Matrix] When the cured product of the present invention is used as a black matrix, the width and shape of the black matrix are appropriately adjusted according to the specifications of the color filter to which it is applied. The black matrix may be created on an array or on a counter substrate.

[0218] [Partition wall, photoconversion layer containing luminescent nanocrystalline particles, color filter] The cured product of the present invention can be used as a partition wall, and can also be used in photoconversion layers and color filters containing luminescent nanocrystalline particles. For example, the patterned cured material manufactured by the method described above can be used in a color filter having partitions, with pixels formed in the regions partitioned by the partitions. Examples of pixel layers include layers containing colored pigments and layers containing luminescent nanocrystalline particles. When using luminescent nanocrystalline particles, the emission color can be selected by changing the constituent materials and size. Examples of luminescent nanocrystalline particles include quantum dots. For example, luminescent nanocrystalline particles described in Japanese Patent Publication No. 2019-086745, and photoconversion layers and color filters using them can be cited.

[0219] [Organic electroluminescent element] Furthermore, various organic electroluminescent devices are manufactured using a substrate equipped with patterned cured material manufactured by the method described above as partition walls. The method for forming the organic electroluminescent device is not particularly limited, but preferably, after forming a partition wall pattern on the substrate by the method described above, the organic electroluminescent device is manufactured by forming organic layers such as pixels using a vapor deposition method in which a functional material is sublimated in a vacuum and deposited into the area surrounded by the partition walls on the substrate, or by a wet process such as a casting method, spin coating method, or inkjet printing method. Examples of organic electroluminescent devices include bottom-emission and top-emission types. In bottom emission type semiconductors, for example, a partition wall is formed on a glass substrate with stacked transparent electrodes, and a hole transport layer, light-emitting layer, electron transport layer, and metal electrode layer are stacked in the opening surrounded by the partition wall. On the other hand, in top emission type semiconductors, for example, a partition wall is formed on a glass substrate with stacked metal electrode layers, and an electron transport layer, light-emitting layer, hole transport layer, and transparent electrode layer are stacked in the opening surrounded by the partition wall.

[0220] As the light-emitting layer, examples include organic electroluminescent layers as described in Japanese Patent Publication No. 2009-146691 and Japanese Patent No. 5734681. Alternatively, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used. The layer configuration is not limited to this; for example, the hole transport layer and electron transport layer may be stacked in a multilayer configuration consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

[0221] Organic electroluminescent elements may be formed with each RGB color separated into different apertures, or two or more colors may be stacked in a single aperture. From the viewpoint of improving reliability, organic electroluminescent elements may be provided with a sealing layer. The sealing layer has the function of preventing moisture in the air from adsorbing onto the organic electroluminescent element and reducing its luminous efficiency. From the viewpoint of improving light extraction efficiency, organic electroluminescent elements may be provided with a low-reflection film at the interface with air. By placing a low-reflection film at the interface between air and the element, it is expected that the refractive index gap will be reduced and reflection at the interface will be suppressed. For example, moth-eye structures and ultra-multilayer film technologies can be applied to such low-reflection films. When using organic electroluminescent elements as pixels in an image display device, it is necessary to prevent light from the light-emitting layer of one pixel from leaking to other pixels. Furthermore, if the electrodes and other components are made of metal, it is necessary to prevent a decrease in image quality due to reflection of ambient light. Therefore, it is preferable to provide light-shielding properties to the partitions that constitute the organic electroluminescent elements. Furthermore, in organic electroluminescent devices, electrodes must be provided on the upper and lower surfaces of the partition wall; therefore, from the viewpoint of insulation, it is preferable for the partition wall to have high resistance and low dielectric constant. For this reason, when using a coloring agent to provide light-shielding properties to the partition wall, it is preferable to use the aforementioned organic pigment which has high resistance and low dielectric constant.

[0222] <<The present invention: an image display device>> An image display device according to one embodiment of the present invention (referred to as the "present invention image display device") includes the cured product of the present invention.

[0223] For example, by placing the black matrix formed from the polymerizable composition of the present invention on a liquid crystal drive substrate (array substrate) or on the counter electrode substrate side, bonding these together to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell, an image display device such as a liquid crystal display device containing the cured product of the present invention can be manufactured.

[0224] Furthermore, a color filter having a black matrix formed from the polymerizable composition of the present invention can also be used as a sub-pixel in an organic light-emitting display panel. Compared to a polarizing plate, the color filter layer can increase the light extraction rate and extend the service life of the organic light-emitting display device. For example, it can be used in the display devices described in Japanese Patent Publication No. 2021-517333 and Japanese Patent Application Publication No. 2021-110936.

[0225] Examples of image display devices of the present invention include organic EL display devices having partitions containing the cured product of the present invention or organic electroluminescent light-emitting devices. As long as the organic electroluminescent display device includes the organic electroluminescent element described above, there are no particular restrictions on the type or structure of the image display device. For example, it can be assembled using an actively driven organic electroluminescent element according to conventional methods. For example, it can be formed by the method described in "Organic EL Display" (Ohmsha, published August 20, 2004, authored by Shizuka Tokito, Chihaya Adachi, and Hideyuki Murata). For example, an image may be displayed by combining an organic electroluminescent element that emits white light with a color filter, or by combining organic electroluminescent elements with different emission colors such as RGB.

[0226] <Other uses> The O-iminoisourea compounds of the present invention generate N radicals upon heating, and sequential decomposition of the resulting N radicals yields alkoxy radicals. These alkoxy radicals can be radically added to polymerizable compounds such as acrylic esters and styrene derivatives. Therefore, the O-iminoisourea compounds of the present invention can be used as thermal polymerization initiators. The aforementioned alkoxy radicals can also be used in hydrogen abstraction reactions, which radically abstract hydrogen from polymers that do not exhibit polymerization reactivity, thereby providing radical reaction sites within the polymer chain. The radical reaction sites generated within the polymer chain bond with each other to form a crosslinked structure, increasing the polymer molecular weight and resulting in improved cohesiveness, mechanical strength, and heat resistance. From this perspective, the O-iminoisourea compound of the present invention can be used as an additive to acrylate polymers used in optical adhesive layer (OCA) materials and polyethylene used in electrical wire and cable coatings, etc., as it is a polymer that does not undergo polymerization reactivity. This increases the molecular weight of these polymers, thereby improving their mechanical strength and heat resistance as described above. On the other hand, the O-iminoisourea compound of the present invention can also be used to reduce the molecular weight by cleaving the main chain through the β-cleavage reaction of radicals in the polymer chain. Since the reduced molecular weight lowers the polymer melting point and improves moldability, it can be suitably used, for example, to improve the moldability of polypropylene or to manufacture polypropylene nonwoven fabrics. The effect of the O-iminoisourea compound of the present invention described above, which increases the polymer molecular weight, is exhibited under relatively low temperature conditions of room temperature to about 150°C in the presence of a radical initiator, while the effect of decreasing the polymer molecular weight is exhibited under conditions of 200°C or higher, where the thermal decomposition of radicals becomes dominant.

[0227] <Explanation of terms, etc.> In this invention, when "α~β" (where α and β are arbitrary numbers) is written, unless otherwise specified, it means "α or greater and β or less," and also includes the meaning of "preferably greater than α" or "preferably less than β." Furthermore, when written as "α or greater" or "α ≤" (where α is any number), unless otherwise specified, it includes the meaning of "preferably greater than α," and when written as "β or less" or "≤β" (where β is any number), unless otherwise specified, it also includes the meaning of "preferably less than β." In the present invention, "A and / or B" means either A and B or both, and specifically means A, B, or A and B.

[0228] In this invention, "(meth)acrylic" means "acrylic and / or methacrylic." In this invention, "total solids" means all components other than the solvent in the polymerizable composition, and even if the components other than the solvent are liquid at room temperature, those components are not included in the solvent but are included in the total solids. In the present invention, "(co)polymer" means including both monopolymers (homopolymers) and copolymers, and "polybasic acid (anhydride)" means "polybasic acid and / or polybasic acid anhydride." In the present invention, the term "weight average molecular weight" means the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography). In the present invention, the term "partition wall" refers to a bank material, a wall material, and a wall member, and similarly, the partition wall refers to a bank, a wall, and a wall structure.

Examples

[0229] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0230] <Synthesis of O-iminoisourea (a)> O-iminoisourea (a) was synthesized according to the following scheme.

[0231] TIFF2026167655000032.tif62170

[0232] (Synthesis Step a-1 Synthesis of benzaldehyde oxime) A stirrer bar was placed in a 100 mL three-necked flask, which was fitted with a dropping funnel and a thermometer. 4.00 g (57.6 mmol) of hydroxylamine hydrochloride and 30 mL of 5% NaOH aqueous solution were added, followed by stirring in a water bath. A solution of 4.8 mL (5.0 g, 47.1 mmol) of benzaldehyde and 20 mL of ethanol was charged into the dropping funnel, and added dropwise while maintaining the internal temperature at 10°C or lower. After completion of the dropwise addition, the reaction was carried out for 30 minutes. Ethanol was distilled off, dichloromethane was added to the residue for phase separation, and the aqueous phase was extracted with dichloromethane. Meanwhile, the organic phase was washed with saturated brine, the collected organic phase was dehydrated with anhydrous sodium sulfate, and then the desiccant was filtered off. The filtrate was concentrated and vacuum-dried to obtain benzaldehyde oxime as a colorless transparent oily substance. The yield was 5.46 g (45.1 mmol), and the yield percentage was 95.7%.

[0233] (Synthesis Step a-2 Synthesis of benzaldehyde oxime chloride) A rotator was placed in a 200 mL three-necked flask, and a dropping funnel, thermometer, and a three-way stopcock connected to a nitrogen line were attached. The reactor was then purged with nitrogen. 5.08 g (41.9 mmol) of benzaldehyde oxime obtained in synthesis a-1 and 30 mL of DMF were added and stirred at room temperature. A solution of 5.60 g (41.9 mmol) of N-chlorosuccinimide and 50 mL of DMF was added dropwise from the dropping funnel at room temperature and reacted at room temperature for 3 hours. Demineralized water and dichloromethane were added to the reaction mixture to separate the phases. The aqueous phase was extracted with dichloromethane, and the oil phase was combined and washed sequentially with demineralized water and saturated brine. The mixture was then concentrated using an evaporator. The concentrated residue was dissolved in toluene and washed with demineralized water to remove the DMF. The oil phase was dehydrated with anhydrous sodium sulfate, the drying agent was filtered off, and the concentrated residue was purified by column chromatography (SiO2 (neutral, spherical), dichloromethane) to obtain pale yellow oily benzaldehyde oxime chloride. The yield was 5.17 g (3.3 mmol), and the yield was 79.3%.

[0234] (Synthesis step a-3 Synthesis of benzaldehyde oxime chloride TBS ether) A rotator was placed in a 50 mL three-necked flask, and a septum cap and a three-way stopcock connected to a nitrogen line were attached. 1.16 g (7.2 mmol) of butyldimethylsilyl chloride and 10 mL of anhydrous DMF were added to the reactor and dissolved. A mixture of 0.92 g (5.9 mmol) of benzaldehyde oxime chloride obtained in synthesis a-2, 15 mL of anhydrous DMF, and 1.6 mL (11.5 mmol) of Et3N was added and the mixture was reacted at room temperature for 2 hours. Demineralized water and toluene were added to the reaction mixture to separate the phases. The aqueous phase was extracted with toluene, and the oil phase was washed with demineralized water. After dehydration with anhydrous magnesium sulfate, the drying agent was filtered off. The filtrate was concentrated using an evaporator to obtain a pale yellow oily substance, benzaldehyde oxime chloride TBS ether. The yield was 1.39 g (5.2 mmol), and the yield rate was 87.4%.

[0235] The obtained compounds were subjected to NMR spectroscopy and structural confirmation by GC-MS. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.90-7.85(m,2H,Ph 2,6-H),7.46-7.36(m,3H,Ph 3,4,5-H),1.00(s,9H,SitBu),0.28(s,6H,SiMe2) GC-MS (CI, NH3) calculated value C 13 H2OClNOSi:269.1, observed value 270.2:[M + H] +

[0236] (Synthesis step a-4 Synthesis of t-butyl-benzohydroxamate) A rotor was placed in a dry 50 mL branched flask, and a three-way stopcock connected to a nitrogen line was attached. 0.96 g (8.5 mmol) of tBuOK and 10 mL of anhydrous DMF were added and stirred in a water bath. A solution of 1.33 g (4.9 mmol) of benzaldehyde oxime chloride TBS ether obtained in synthesis a-3 and 10 mL of anhydrous DMF was added by syringe, and the reaction was carried out in a water bath for 2 hours. Desalted water and toluene were added to separate the phases. The aqueous phase was extracted with toluene, and the recovered oil phase was dehydrated with anhydrous magnesium sulfate. The drying agent was filtered off. The filtrate was concentrated under reduced pressure to obtain pale yellow oily t-butyl-benzohydroxamate. The yield was 0.93 g (4.8 mmol), and the yield was 98.0%.

[0237] The obtained compounds were subjected to NMR spectroscopy and structural confirmation by GC-MS. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.69-7.63(m,2H,Ph 2,6-H),7.43-7.33(m,3H,Ph 3,4,5-H,OH),1.40(s,9H,OtBu) GC-MS (CI, NH3) calculated value C 11 H 15 NO2: 193.1, Observed value 194.2: [M + H] +

[0238] (Synthesis process a-5 Synthesis of O-iminoisourea(a)) A rotor was placed in a dry 200 mL four-neck flask, and a three-way stopcock connected to a nitrogen line and a thermometer were attached. 0.26 g (5.8 mmol) of sodium hydride (oil-based 55%) and 10 mL of anhydrous THF were added and stirred in an ice bath. From a syringe, a solution of 1.095 g (5.7 mmol) of t-butyl-benzohydroxamate obtained in synthesis a-4 and 10 mL of anhydrous THF was added. After the foaming subsided, a solution of 0.75 g (5.9 mmol) of N,N'-diisopropylcarbodiimide and 10 mL of anhydrous THF was added. After the addition, the ice bath was removed, and the mixture was reacted at an internal temperature of 20°C for 2 hours, and then in an oil bath at an internal temperature of 40°C for 7 hours. The mixture was cooled in an ice bath, and iPrOH was added to decompose the unreacted sodium hydride. The reaction mixture was then concentrated under reduced pressure. Demineralized water and dichloromethane were added to the concentrated residue to separate the phases. The aqueous phase was extracted with dichloromethane, and the recovered oil phase was sequentially washed with demineralized water and saturated brine. After dehydrating the oil phase with anhydrous sodium sulfate, the drying agent was filtered off, and the mixture was concentrated under reduced pressure to obtain the crude product. This crude product was subjected to column chromatography (amine-modified SiO2 (Fuji Silycia Chromatorex NH-DM1020: particle size 100 μm, specific surface area 250 m²)). 2 The solution was purified with hexane / ethyl acetate (10 / 1) at a pore size of 16 nm to obtain colorless, transparent oily O-iminoisourea (a). The yield was 0.84 g (2.6 mmol), and the yield was 46.6%.

[0239] The obtained compounds were subjected to NMR spectroscopy and structural confirmation by LC-MS. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.69(dd,J=8.8Hz,2H),7.45(t,J=7.2Hz,1H),7.40(t,J=8.0Hz,2H),5.09(br,1H),4.06(br,1H),3.84(br,1H),1.39(s,9H),1.15(br,12H) LCMS(ESI + ): m / z calculated value C 18 H 29 N3O2: 319.2, observed value 320.2: [M + H] +

[0240] <Synthesis of O-iminoisourea (b)> O-iminoisourea (b) was synthesized according to the following flow.

[0241] TIFF2026167655000033.tif56170

[0242] A stirrer bar was placed in a dry 200 mL four-necked flask, which was fitted with a three-way stopcock connected to a nitrogen line and a thermometer. 0.25 g (5.7 mmol) of sodium hydride (55% in oil) and 10 mL of dehydrated THF were added, and the mixture was stirred in an ice bath. A solution of 1.02 g (5.7 mmol) of t-butyl-benzohydroxamate obtained in the same manner as in Synthesis a-4 and 10 mL of dehydrated THF was added from a syringe, the mixture was stirred for 5 minutes, and then a solution of 1.19 g (5.8 mmol) of N,N'-dicyclohexylcarbodiimide and 10 mL of dehydrated THF was added. The mixture was allowed to react at an internal temperature of 5°C for 1 hour, at room temperature for 2 hours, and in an oil bath at an internal temperature of 50°C for 5 hours. The reaction mixture was cooled, iPrOH was added to decompose unreacted sodium hydride, and then the reaction mixture was concentrated under reduced pressure. Demineralized water and dichloromethane were added to the concentrated residue for phase separation, the aqueous phase was extracted with dichloromethane, the collected organic phase was washed sequentially with demineralized water and saturated brine, and the organic phase was dehydrated over anhydrous sodium sulfate. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. This crude product was purified by column chromatography (amine-modified SiO₂, Fuji Silysia Chromatorex NH-DM1020, hexane / ethyl acetate = 10 / 1) to obtain O-iminoisourea (b) as a colorless transparent oily substance. The yield was 0.71 g (1.8 mmol), and the yield percentage was 33.8%.

[0243] The obtained compound was subjected to NMR spectrum measurement and structural confirmation by LC-MS. The results are shown below. 1H-NMR (CDCl3) δ (ppm) 7.69 (dd, J=8.8Hz, 2H), 7.45 (t, J=7.2Hz, 1H), 7.39 (t, J=8.0Hz, 2H), 5.20 (br, 1H), 3.66 (br, 1H), 3.55 (br, 1H), 3.26-3.14 (m, 1H), 2.11-1.97 (m, 2H), 1.97-1.88 (m, 2H), 1.82-1.52 (m, 5H), 1.45-1.04 (m, 10H), 1.41 (s, 9H) LCMS (ESI + ): m / z calculated value C 24 H 37 N3O2: 399.3, observed value 400.3: [M + H] +

[0244] <Synthesis of O-iminoisourea (c)> O-iminoisourea (c) was synthesized according to the following scheme.

[0245] TIFF2026167655000034.tif50170

[0246] A stir bar was placed in a dry 200 mL four-necked flask, which was fitted with a thermometer and a three-way stopcock connected to a nitrogen line. To this were added 0.23 g (5.3 mmol) of sodium hydride (55% in oil) and 10 mL of dehydrated THF, followed by stirring in an ice bath. A solution of 0.97 g (5.0 mmol) of t-butyl-benzohydroxamate obtained in the same manner as in Synthesis a-4 and 10 mL of dehydrated THF was added via syringe, and then a solution of 1.88 g (5.2 mmol) of bis(2,6-iPr2Ph)2carbodiimide and 10 mL of dehydrated THF was added sequentially. The reaction was carried out for 5 minutes in an ice bath, 30 minutes in a water bath, and then allowed to warm to room temperature for 1 hour. Under cooling, isopropyl alcohol was added to deactivate sodium hydride, and the reaction mixture was concentrated under reduced pressure. Demineralized water and dichloromethane were added to the concentrated residue for phase separation, the aqueous phase was extracted with dichloromethane, the collected oil phase was washed with saturated brine, dehydrated with anhydrous sodium sulfate, then the desiccant was filtered off and the filtrate was concentrated under reduced pressure. The recovered product was purified by column chromatography (SiO2 (spherical neutral), dichloromethane) to recover a white scaly solid, which was further washed with hexane as a solvent to obtain O-iminoisourea (c) as a white solid. The yield was 1.07 g (1.9 mmol), and the yield rate was 38.6%.

[0247] The obtained compound was subjected to structural confirmation by NMR spectrum measurement and LC-MS. The results are shown below. 1H-NMR (CDCl3) δ (ppm) 7.75 (dd, J=8.4Hz, 2H), 7.45 (t, J=7.2Hz, 1H), 7.38 (t, J=8.0Hz, 2H), 7.29 (t, J=6.8Hz, 1H), 7.22 (d, J=7.6Hz, 2H), 7.04 (br, 1H), 7.75 (d, J=7.6Hz, 2H), 6.89 (t, J=7.2Hz, 1H), 3.51 (m, 2H), 3.13 (m, 2H), 1.22 (d, J=7.2Hz, 6H), 1.09 (d, J=6.8Hz, 6H), 0.97 (s, 9H) LCMS(ESI + ): m / z calculated value C 36 H 49 N3O2: 555.4, observed value 556.4: [M + H] +

[0248] <Synthesis of O-iminoisourea (d)> O-iminoisourea (d) was synthesized according to the following flow.

[0249] TIFF2026167655000035.tif66170

[0250] (Synthesis Step d-1 Synthesis of 4-trifluoromethylbenzaldoxime) A rotator was placed in a 500 mL three-necked flask, and a dropping funnel and temperature indicator were attached. 8.7 g (218 mmol) of sodium hydroxide and 100 mL of desalted water were added, and the mixture was cooled in an ice bath. 12.05 g (173 mmol) of hydroxylamine hydrochloride was added and dissolved. While maintaining the internal temperature below 10°C, a solution of 25.0 g (144 mmol) of 4-trifluoromethylbenzaldehyde and 70 mL of ethanol was added via the dropping funnel over 30 minutes, and the mixture was reacted in an ice bath for 3 hours. The precipitated solid was recovered by suction filtration, and the filtrate was concentrated under reduced pressure. The concentrated residue was extracted with dichloromethane. The recovered solid and the extracted oil phase were combined, and dichloromethane was added to form a solution, which was then washed sequentially with desalinated water and saturated brine. The oil phase was dehydrated with anhydrous sodium sulfate, and the drying agent was filtered off. The filtrate was concentrated under reduced pressure, and hexane was added to the concentrated residue to obtain the precipitated white crystalline solid, 4-trifluoromethylbenzaldehyde oxime. The yield was 20.69 g (109 mmol), and the yield rate was 76.2%.

[0251] (Synthesis step d-2: Synthesis of 4-trifluoromethylbenzaldehyde oxime chloride) A rotator was placed in a 300 mL three-necked flask, and a dropping funnel, thermometer, and a three-way stopcock connected to a nitrogen line were attached. 10.03 g (53.0 mmol) of 4-trifluoromethylbenzaldehyde oxime obtained in synthesis d-1 and 100 mL of DMF were added and stirred in an ice bath. A solution of 7.80 g (58.4 mmol) of N-chlorosuccinimide and 50 mL of DMF was added dropwise from the dropping funnel, maintaining an internal temperature of 10°C. After the addition was complete, the temperature was raised to room temperature and the reaction was allowed to proceed for 2 hours. The reaction mixture was cooled in an ice bath, and demineralized water and dichloromethane were added. The separated oil phase was collected, and the aqueous phase was extracted with dichloromethane. The oil phases were combined and concentrated under reduced pressure, and the residue was dissolved in toluene and washed sequentially with demineralized water and saturated brine. The oil phase was dehydrated with anhydrous sodium sulfate, and the liquid after filtering off the drying agent was concentrated under reduced pressure to obtain pale yellow oily 4-trifluoromethylbenzaldehyde oxime chloride. The yield was 11.0 g (49.1 mmol), and the yield rate was 92.5%.

[0252] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)9.24(s,1H,OH),7.98(d,J=8,4Hz,2H,Ph-2,6H),7.66(d,J=8,4Hz,2H,Ph-3,5H)

[0253] (Synthesis step d-3: Synthesis of 4-trifluoromethylbenzaldehyde oxime chloride TBS ether) A rotator was placed in a 100 mL three-necked flask, and a septum cap, thermometer, and a three-way stopcock connected to a nitrogen line were attached. 2.04 g (9.1 mmol) of 4-trifluoromethylbenzaldehyde oxime chloride obtained in synthesis d-2, 2.06 g (13.7 mmol) of t-butyldimethylsilyl chloride, and 30 mL of DMF were added and dissolved, and the mixture was cooled and stirred in an ice bath. Maintaining the internal temperature below 10°C, 2.5 mL (17.9 mmol) of triethylamine was added, and the mixture was reacted in an ice bath for 4 hours. Toluene and demineralized water were added, the separated oil phase was collected, and the aqueous phase was extracted with toluene. The oil phase was combined and washed sequentially with demineralized water and saturated brine. The oil phase was dehydrated with anhydrous sodium sulfate, the drying agent was filtered off, and the crude product was obtained by vacuum concentration. The crude product was purified by column chromatography (SiO2 (spherical neutral), hexane) to obtain pale yellow oily 4-trifluoromethylbenzaldehyde oxime chloride TBS ether. The yield was 3.00 g, and the yield was 97.5%.

[0254] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.97(d,J=8.0Hz,2H,Ph-2,6H),7.63(d,J=8,0Hz,2H,Ph-3,5H),0.99(s,9Hz,Si-tBu),0.27(s,6Hz,Si-Me2)

[0255] (Synthesis step d-4: Synthesis of butyl-4-trifluoromethylbenzohydroxamate) A rotor was placed in a dry 100 mL three-necked flask, and a three-way stopcock connected to a thermometer and nitrogen line was attached. 1.16 g (10.3 mmol) of tBuOK and 15 mL of anhydrous DMF were added and stirred in an ice bath. A solution of 1.99 g (5.9 mmol) of 4-trifluoromethylbenzaldehyde oxime chloride TBS ether obtained in synthesis d-3 and 15 mL of dry DMF was added, and the reaction was carried out in an ice bath for 2 hours. Toluene and demineralized water were added to the reaction mixture to separate the oil phase, and the aqueous phase was extracted with toluene. The oil phase was sequentially washed with demineralized water and saturated brine, and after dehydration with anhydrous sodium sulfate, the drying agent was filtered off. The residue obtained by concentrated under reduced pressure was purified by column chromatography (SiO2 (spherical neutral), hexane:ethyl acetate = 5:1) to obtain pale yellow oily t-butyl-4-trifluoromethylbenzohydroxamate. The yield was 1.61 g (6.2 mmol), and the yield was 59.9%.

[0256] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.80(d,J=8.0Hz,2H,Ph-2,6H),7.63(d,J=8,0Hz,2H,Ph-3,5H),7.47(s,1Hz,OH),1.42(s,9Hz,OtBu)

[0257] (Synthesis process d-5 Synthesis of O-iminoisourea(d)) A rotor was placed in a dry 50 mL three-necked flask, and a thermometer and a three-way stopcock connected to a nitrogen line were attached. 0.21 g (4.7 mmol) of 55% oily sodium hydride was added, and the mineral oil was washed off with dehydrated hexane. 4 mL of dehydrated THF was added and stirred in an ice bath, and then a solution of 0.82 g (3.1 mmol) of t-butyl-4-trifluoromethylbenzohydroxamate synthesized in synthesis d-4 and 5 mL of dehydrated THF was added. After the foaming subsided, a solution of 1.34 g (3.7 mmol) of bis(2,6-iPrphenyl)carbodiimide and 6 mL of THF was added, and the mixture was reacted in an ice bath for 1.5 hours and at room temperature for 4 hours. 2-Propanol was added to decompose unreacted sodium hydride. Toluene and demineralized water were added, the separated oil phase was collected, and the aqueous phase was extracted with toluene. The combined oil phases were washed sequentially with demineralized water and saturated brine, dehydrated over anhydrous sodium sulfate, and the desiccant was filtered off. The recovered residue obtained by concentration under reduced pressure was purified by column chromatography (SiO₂ (spherical neutral), hexane:dichloromethane=1:1) to obtain O-iminoisourea (d) as a white solid. The yield was 1.37 g (2.2 mmol), and the yield rate was 70.2%.

[0258] The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below. 1H-NMR(CDCl₃) δ(ppm)7.83(d,J=8.0Hz,2H,Ph-2,6H),7.65(d,J=8.0Hz,2H,Ph-3,5H),7.37-7.28(m,1H,N-Ph 4H),7.22(d,J=7.6Hz,2H,N-Ph 3H),6.99(d,J=7.2Hz,2H,N-Ph 5H),6.95-6.87(m,1H,N-Ph'4H-2),3.55-3.44(m,2H,iPr-CHMe₂),3.19-3.06(m,2H,iPr-CHMe₂'),1.22(d,J=6.8Hz,6H,iPr-CHMe₂),1.09(d,J=6.8Hz,6H,iPr-CHMe₂'),0.98(s,9H,OtBu)

[0259] <Synthesis of O-iminoisourea (e)> O-iminoisourea (E) was synthesized according to the following flow.

[0260] TIFF2026167655000036.tif63170

[0261] (Synthesis Step e-1 Synthesis of 4-Methoxybenzaldoxime) A stagger was placed in a 500 mL three-necked flask, and a dropping funnel and thermometer were attached. A solution of 12.4 g (310 mmol) of sodium hydroxide and 120 mL of desalted water was added and cooled in an ice bath. 17.20 g (247 mmol) of hydroxylamine hydrochloride was added and dissolved. While maintaining the internal temperature below 10°C, a solution of 25 mL (206 mmol) of 4-methoxybenzaldehyde and 80 mL of ethanol was added via the dropping funnel over 20 minutes and the mixture was allowed to react for 1 hour. The reaction mixture was partially concentrated, and the oil phase was separated by adding desalted water and dichloromethane. The aqueous phase was extracted with dichloromethane, and the combined aqueous and oil phases were concentrated under reduced pressure. The concentrated residue was sonicated to obtain solidified 4-methoxybenzaldehyde oxime as a white crystalline solid. The yield was 29.4 g (195 mmol), with a yield of 94.5%.

[0262] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm) 8.10(s,1H,CH=N),7.98(s,1H,OH),7.52(dd,J=8.8Hz,2H,(MeOPh) 2,6-H),6.91(dd,J=8.8Hz,2H,Ph 3,5-H),3.83(s,3H, OMe)

[0263] (Synthesis step e-2: Synthesis of 4-methoxybenzaldehyde oxime chloride) A stagger was placed in a 300 mL three-necked flask, and a dropping funnel, thermometer, and a three-way stopcock connected to an N2 line were attached. 10.02 g (66.3 mmol) of 4-methoxybenzaldehyde oxime obtained in synthesis e-1 and 80 mL of DMF were added and stirred in an ice bath. Maintaining the internal temperature below 10°C, a solution of 9.73 g (72.9 mmol) of N-chlorosuccinimide and 40 mL of DMF was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted for 30 minutes at an internal temperature of 10°C, followed by 2 hours at room temperature. Toluene and demineralized water were added to the reaction mixture to separate the oil phase, and the aqueous phase was extracted with toluene. The oil phases were combined and washed sequentially with demineralized water and saturated brine, then dehydrated with anhydrous sodium sulfate, and the drying agent was filtered off. The filtrate was concentrated under reduced pressure to obtain pale yellow oily 4-methoxybenzaldehyde oxime chloride. The yield was 8.54 g (46.0 mmol), and the yield was 70.0%.

[0264] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)8.97(s,1H,OH),7.79(dd,J=9.2Hz,2H,Ph-3,5H),6.91(d,J=9.2Hz,2H,Ph-2,6H),3.84(s,3H, OMe)

[0265] (Synthesis step e-3: Synthesis of 4-methoxybenzaldehyde oxime chloride TBS ether) A stagger was placed in a 200 mL three-necked flask, and a thermometer and a three-way stopcock connected to an N2 line were attached. 6.00 g (32.3 mmol) of 4-methoxybenzaldehyde oxime chloride obtained in synthesis e-2 and 50 mL of DMF were added and stirred in an ice bath, to which 5.81 g (38.5 mmol) of t-butyldimethylsilyl chloride was added. While maintaining the internal temperature below 10°C, 8.0 mL (57.4 mmol) of triethylamine was added, and the mixture was reacted at 10°C for 1 hour, and then at room temperature for 6 hours. Toluene and demineralized water were added to the reaction mixture to recover the oil phase, and the aqueous phase was extracted with toluene. The oil phases were combined and washed sequentially with demineralized water and saturated brine, dehydrated with anhydrous sodium sulfate, and the drying agent was filtered off. The filtrate was concentrated to obtain a crude product which was purified by column chromatography (SiO2 (spherical neutral), hexane:ethyl acetate = 20:1) to obtain pale yellow oily 4-methoxybenzaldehyde oxime chloride TBS ether. The yield was 9.70 g (32.3 mmol), and the yield was 100%.

[0266] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.81(dd,J=9.2Hz,2H,Ph-3,5H),6.91(dd,J=9.2Hz,2H,Ph-2,6H),3.84(s,3H,OMe),0.99(s,9H,Si-tBu),0.27(s,6H,Si-Me2)

[0267] (Synthesis step e-4 Synthesis of t-butyl-4-methoxybenzohydroxamate) A rotor was placed in a dry 100 mL three-necked flask, and a septum cap and a three-way stopcock connected to a nitrogen line were attached. 2.00 g (17.8 mmol) of potassium tBuOK and 15 mL of dry DMF were added and stirred in an ice bath. A solution of 3.03 g (10.1 mmol) of 4-methoxybenzaldehyde oxime chloride TBS ether synthesized in synthesis e-3 and 10 mL of dry DMF was added, and the mixture was reacted in an ice bath for 1 hour and at room temperature for 2 hours. Demineralized water and toluene were added to the reaction mixture, the separated oil phase was collected, and the aqueous phase was extracted with toluene. The collected oil phases were combined and washed sequentially with demineralized water and saturated brine, then dehydrated with anhydrous sodium sulfate and separated. The crude product obtained by vacuum concentration was purified by column chromatography (SiO2 (spherical neutral), hexane:ethyl acetate = 5:1) to obtain t-butyl-4-methoxybenzohydroxamate as a white solid. The yield was 1.76 g (7.9 mmol), and the yield rate was 77.9%.

[0268] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.59(dd,J=8.8Hz,2H,Ph-3,5H),7.41(s,1H,OH),6.89(dd,J=8.8Hz,2H,Ph-2,6H),3.83(s,3H,OMe),1.40(s,9H,OtB

[0269] (Synthesis step e-5 Synthesis of O-iminoisourea(e)) A rotor was placed in a 50 mL branched flask, and a three-way cock connected to a N2 line was attached. 0.75 g (3.4 mmol) of tert-butyl 4-methoxybenzohydroxamate obtained in Synthesis e-4, 1.60 g (4.4 mmol) of bis(2,6-diisopropylphenyl)carbodiimide, and 10 mL of THF were added, followed by stirring at room temperature. To this was added 0.05 g (1.3 mmol) of NaOH (granular), and the mixture was reacted at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure, and 5 mL of dichloromethane was added to the residue to form a suspension. Insoluble matter was removed using a 0.45 μm PTFE filter, and the filtrate was concentrated under reduced pressure. The concentrated residue was purified by column chromatography (amine-modified SiO2 (Fuji Silysia Chromatorex NH-DM1020), hexane / ethyl acetate = 20 / 1) to obtain O-iminoisourea (e) as an amorphous white solid. The yield was 1.33 g (2.3 mmol), and the yield rate was 67.8%.

[0270] Structural confirmation of the obtained compound was performed by NMR spectrum measurement. The results are shown below. 1H-NMR (CDCl3) δ (ppm) 7.64 (d, J=8.8Hz, 2H, (MeO)Ph-3,5H), 7.29 (t, J=8.0Hz, 1H, NPh 4H), 7.21 (d, J=7.6Hz, 2H, (MeO)Ph-2,6H), 7.06 (s, 1H, NH), 6.98 (d, J=7.6Hz, 2H, N-Ph 3,3'H), 6.91-6.86 (m, 3H, N-Ph 5,5',4'H), 3.83 (s, 3H, OMe), 3.58-3.43 (m, 2H, iPr-CHMe2), 3.21-3.07 (m, 2H, iPr-CHMe2'), 1.22 (d, J=7.2Hz, 6H, iPr-CHMe2), 1.08 (d, J=6.8Hz, 6H, iPr-CHMe2'), 0.96 (s, 9H, OtBu)

[0271] <Synthesis of O-iminoisourea (f)> O-iminoisourea (f) was synthesized according to the following flow.

[0272] TIFF2026167655000037.tif69170

[0273] (Synthesis step f-1: Synthesis of 4-pyridylaldehyde oxime) A stagger was placed in a 500 mL three-necked flask, and a dropping funnel and thermometer were attached. 200 mL of 1 mol / L sodium hydroxide aqueous solution was added and cooled in an ice bath. A solution of 22.24 g (320 mmol) of hydroxylamine hydrochloride and 50 mL of demineralized water was added. Maintaining the internal temperature below 10°C, a solution of 28.5 g (266 mmol) of 4-pyridinecarboxaldehyde, 50 mL of demineralized water, and 50 mL of ethanol was added dropwise from the dropping funnel over 20 minutes. The mixture was allowed to react in an ice bath for 30 minutes, then raised to room temperature and allowed to react for 2 hours. The precipitated solid was collected by suction filtration, and the filtrate was concentrated under reduced pressure until it reached approximately 100 mL. Dichloromethane and demineralized water were added to the concentrated residue to separate the phases, and the aqueous phase was extracted with dichloromethane. The previously collected solid and the concentrated oil phase were combined and washed with hexane to obtain 4-pyridylaldehyde oxime, a white crystalline solid. The yield was 20.59 g (169 mmol), and the yield rate was 63.3%.

[0274] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm) 10.74(s,1H,OH),8.65(dd,J=6.4Hz,2H,Py 3,5-H),8.13(s,1H,N=CH),7.53(dd,J=6.0Hz,2H,Py-2,6)

[0275] (Synthesis step f-2: Synthesis of 4-pyridylaldehyde oxime chloride) A stagger was placed in a 200 mL three-necked flask, and a dropping funnel, thermometer, and a three-way stopcock connected to a nitrogen line were attached. 10.0 g (81.9 mmol) of 4-pyridylaldehyde oxime synthesized in f-1 and 30 mL of DMF were added to the flask and stirred at room temperature. A solution of 13.18 g (9.9 mmol) of N-chlorosuccinimide and 50 mL of DMF was added dropwise from the dropping funnel at room temperature over 40 minutes, and the mixture was allowed to react at room temperature for 2 hours. The reaction mixture was cooled on ice, and the precipitated solid was collected by suction filtration after adding desalted water. The collected solid was washed with acetonitrile to obtain 4-pyridylaldehyde oxime chloride, a white crystalline solid. The yield was 5.52 g (35.3 mmol), and the yield rate was 43.1%.

[0276] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)12.9(s,1H,OH),8.62(dd,J=6.0Hz,2H,Ph-3,5H),7.67(d,J=6.0Hz,2H,Ph-2,6H)

[0277] (Synthesis step f-3: Synthesis of 4-pyridylaldehyde oxime chloride TBS ether) A stabilizer was placed in a 200 mL three-necked flask, and a dropping funnel and a three-way stopcock connected to a nitrogen line were attached. 2.50 g (16.0 mmol) of 4-pyridylaldehyde oxime chloride obtained in synthesis F-2 and 2.66 g (17.6 mmol) of t-butyldimethylsilyl chloride were added, followed by 50 mL of DMF, and the mixture was stirred in an ice bath. Maintaining the internal temperature below 10°C, a solution of 3.4 mL (24.4 mmol) of triethylamine and 5 mL of DMF was added from the dropping funnel over 10 minutes, and the mixture was reacted in an ice bath for 2 hours. The oil phase was separated by adding demineralized water and toluene, and the aqueous phase was extracted with toluene. The oil phases were combined and washed sequentially with demineralized water and saturated brine, and after dehydration with anhydrous sodium sulfate, the drying agent was filtered off. The filtrate was concentrated under reduced pressure to recover the crude product, which was purified by column chromatography (SiO2 (spherical neutral), hexane:ethyl acetate = 1:1) to obtain pale yellow oily 4-pyridylaldehyde oxime chloride TBS ether. The yield was 1.46 g (5.4 mmol), and the yield was 33.7%.

[0278] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)8.67(dd,J=6.0Hz,2H,Ph-3,5H),7.63(dd,J=6.4Hz,2H,Ph-2,6H),1.00(s,9Hz,Si-tBu),0.30(s,6Hz,Si-Me2)

[0279] (Synthesis step f-4: Synthesis of butyl-4-pyridinoylhydroxamate) A rotor was placed in a dry 100 mL three-neck flask, and a three-way stopcock connected to a thermometer and nitrogen line was attached. 2.64 g (23.5 mmol) of tBuOK was added, and 15 mL of anhydrous DMF was added and stirred in an ice bath at an internal temperature of 5°C. A solution of 2.04 g (7.5 mmol) of 4-pyridylaldehyde oxime chloride TBS ether synthesized in synthesis f-3 and 15 mL of dry DMF was added and reacted in an ice bath for 1 hour. The oil phase was recovered by adding desalinated water and dichloroethane. Saturated ammonium chloride aqueous solution was added to the aqueous phase to adjust the pH to 8, and the mixture was extracted with dichloromethane. The oil phase was combined with the aqueous phase and washed with saturated brine. After dehydration with anhydrous sodium sulfate, the drying agent was filtered off. The filtrate was concentrated under reduced pressure to obtain the crude product, which was purified by column chromatography (SiO2 (spherical neutral), hexane:ethyl acetate = 1:1) to obtain t-butyl-4-pyridinoylhydroxamate as a pale yellow crystalline solid. The yield was 0.95 g (4.9 mmol), and the yield was 65.3%.

[0280] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)8.64(dd,J=6.4Hz,2H,Ph-3,5H),8.13(s,1H,OH),7.59(dd,J=6,0Hz,2H,Ph-2,6H),1.44(s,9Hz,OtBu)

[0281] (Synthesis process f-5 Synthesis of O-iminoisourea(f)) A rotor was placed in a 50 mL branched flask, and a three-way cock connected to a N₂ line was attached. The inside of the vessel was purged with N₂, 0.77 g (3.9 mmol) of tert-butyl-4-pyridinoylhydroxamate obtained in Synthesis f-4 and 1.77 g (4.9 mmol) of bis(2,6-iPr₂phenyl)carbodiimide were added, 10 mL of THF was added, and the mixture was stirred at room temperature. 0.15 g (3.8 mmol) of sodium hydroxide (granular solid) was added, and the mixture was reacted at room temperature for 3 hours. Insoluble components were removed by suction filtration, the filtrate was concentrated under reduced pressure, and the resulting residue was dissolved in dichloromethane. Insoluble matter was removed using a 0.45 μm Teflon filter. The filtrate was concentrated under reduced pressure, and the resulting residue was washed with hexane to obtain O-iminoisourea (f) as a white crystalline solid. The yield was 1.05 g (1.9 mmol), and the yield rate was 47.6%.

[0282] The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below. ¹H-NMR (CDCl₃) δ (ppm) 8.67 (d, J=5.6 Hz, 2H, Ph-3,5H), 7.58 (d, J=6.0 Hz, 2H, Ph-2,6H), 7.35-7.28 (m, 1H, N-Ph 4H), 7.23 (d, J=7.6 Hz, 2H, N-Ph 3H), 6.99 (d, J=7.6 Hz, 2H, N-Ph 5H), 6.94-6.87 (m, 1H, N-Ph' 4H-2), 3.58-3.42 (m, 2H, iPr-CHMe₂), 3.16-3.04 (m, 2H, iPr-CHMe₂'), 1.21 (d, J=6.4 Hz, 6H, iPr-CHMe₂), 1.09 (d, J=6.8 Hz, 6H, iPr-CHMe₂'), 0.99 (s, 9H, OtBu)

[0283] <Synthesis of O-iminoisourea (g)> O-iminoisourea (g) was synthesized according to the following flow.

[0284] TIFF2026167655000038.tif43170

[0285] (Synthesis Step g-1 Synthesis of methyl-benzohydroxamate) 4.34 g (22.5 mmol) of 28% sodium methoxide / methanol solution and 16 mL of anhydrous methanol were placed in a dry 50 mL four-necked flask and cooled in a water bath. 1.17 g (7.5 mmol) of benzaldehyde oxime chloride synthesized using the same formulation as in synthesis a-2 was added and the mixture was stirred in a water bath for 2 hours. Desalted water and ethyl acetate were added to the reaction mixture to separate the phases, and the aqueous phase was extracted with ethyl acetate. The recovered oil phase was dehydrated with anhydrous sodium sulfate, and the drying agent was filtered off. The filtrate was concentrated under reduced pressure and subsequently vacuum-dried to obtain methyl-benzohydroxamate as a white solid. The yield was 0.64 g (4.2 mmol), and the yield was 56.0%.

[0286] (Synthesis process g-2: Synthesis of O-iminoisourea (g)) A rotor was placed in a 30 mL round-bottom flask, a three-way stopcock connected to a nitrogen line was attached, and the container was purged with nitrogen. 0.53 g (3.5 mmol) of methyl-benzohydroxamate obtained in synthesis g-1 and 9 ml of THF were added and stirred at room temperature. 1.27 g (3.5 mmol) of bis(2,6-iPr2Ph)carbodiimide was added and stirred at room temperature. 0.025 g (0.6 mmol) of granular sodium hydroxide was added and stirred for 1 hour, then allowed to stand for 2 days. Desalted water and ethyl acetate were added to the reaction mixture to separate the phases, and the aqueous phase was extracted with ethyl acetate. The oil phase was combined and dehydrated with anhydrous sodium sulfate, and the drying agent was filtered off. The filtrate was concentrated under reduced pressure, and the resulting crude product was purified using Yamazen Corporation's W-Prep2XY with hexane / chloroform as the developing solvent to obtain a white solid O-iminoisourea (g). The yield was 0.44 g (0.86 mmol), and the yield was 24.6%.

[0287] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR (CDCl3) δ (ppm) 7.74 (d, J=7.2Hz, 2H), 7.45 (t, J=7.6Hz, 1H), 7.37 (t, J=7.6Hz, 2H), 7.32 (t, J=6.8Hz, 1H), 7.24 (d, J=7.6Hz, 2H), 7.11 (br, 1H), 7.01 (d, J=7.6Hz, 2H), 6.92 (t, J=6.8Hz, 1H), 3.58-3.44 (m, 2H), 3.52 (s, 3H), 3.30-3.10 (m, 2H), 1.43-1.04 (m, 12H)

[0288] <Synthesis of O-iminoisourea (h)> O-iminoisourea (h) was synthesized according to the following flow.

[0289] TIFF2026167655000039.tif44170

[0290] (Synthesis Step h-1 Synthesis of acetaldoxime chloride) 1.18 g (20.0 mmol) of acetaldoxime (a commercial product from Tokyo Chemical Industry Co., Ltd.) and 11 mL of DMF were placed in a 50 mL eggplant-shaped flask, followed by stirring at room temperature. 2.80 g (21.0 mmol) of N-chlorosuccinimide was added as a solid, and the mixture was stirred at room temperature for 2 hours. Demineralized water and ethyl acetate were added to the reaction mixture for phase separation, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, washed with demineralized water, dehydrated over anhydrous sodium sulfate, and then the desiccant was filtered off. The filtrate was concentrated under reduced pressure and vacuum-dried to recover a mixture of 2.05 g of acetaldoxime chloride (h-1) and DMF.

[0291] (Synthesis Step h-2 Synthesis of methyl acetohydroxamate) A stirrer bar was placed in a dry 50 mL four-necked flask, and a three-way cock connected to a nitrogen line was attached. 5.79 g (30 mmol) of a 28% sodium methoxide in methanol solution and 20 mL of dehydrated methanol were added, followed by cooling in a water bath. 2.05 g (22.0 mmol) of acetaldoxime chloride obtained in Synthesis h-1 was added, and the mixture was stirred in a water bath for 3 hours and then allowed to stand overnight. Desalted water and ethyl acetate were added to the reaction solution for phase separation, and the aqueous phase was extracted with chloroform. The combined organic phases were dehydrated over anhydrous sodium sulfate, and then the desiccant was removed by filtration. The filtrate was concentrated under reduced pressure and subsequently vacuum-dried to obtain pale yellow oily methyl acetohydroxamate. The yield was 0.69 g (7.7 mmol), corresponding to a 35.0% yield.

[0292] (Synthesis Step h-3: Synthesis of O-iminoisourea (h)) In a 100 mL eggplant-shaped flask, 0.67 g (7.5 mmol) of methyl acetohydroxamate obtained in Synthesis h-2 and 19 mL of THF were placed, followed by stirring at room temperature. 2.18 g (6.0 mmol) of bis(2,6-iPr2Ph)carbodiimide was added, and the mixture was stirred at room temperature. After adding 0.066 g (1.7 mmol) of granular sodium hydroxide and stirring for 2 hours, the mixture was allowed to stand for 3 days. The reaction solution was filtered to remove solids, and the filtrate was concentrated under reduced pressure to obtain 2.64 g of a crude product. This crude product was subjected to column purification using W-Prep 2XY manufactured by Yamazen Corporation with hexane / chloroform as the developing solvent, to obtain O-iminoisourea (h) as a white solid. The yield was 0.18 g (0.4 mmol), corresponding to a 5.3% yield.

[0293] The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below. 1H-NMR (CDCl3) δ (ppm) 7.34-7.2 (m, 1H), 7.21 (d, J=7.2Hz, 2H), 6.99 (d, J=7.2Hz, 2H), 6.95-6.85 (m, 1H), 3.74 (s, 3H), 3.57-3.40 (m, 2H), 3.19-3.02 (m, 2H), 1.72 (s, 3H), 1.43-0.99 (m, 12H)

[0294] <Synthesis of O-iminoisourea (i)> O-iminoisourea (i) was synthesized according to the following scheme.

[0295] TIFF2026167655000040.tif50170

[0296] (Synthesis step i-1: Synthesis of phenylbenzohydroxamate) A rotor was placed in a dry 50 mL branched flask, and a three-way stopcock connected to a nitrogen line was attached. 0.70 g (16.1 mmol) of sodium hydride (oil-based, 55%) and 10 mL of anhydrous THF were added and stirred in an ice bath. A solution of 1.35 g (14.4 mmol) of phenol and 10 mL of anhydrous THF was added and stirred for 10 minutes. A solution of 1.23 g (7.9 mmol) of benzaldehyde oxime chloride obtained in synthesis a-2 and 5 mL of anhydrous THF was added and reacted in an ice bath for 30 minutes, and then at room temperature for 3 hours. Demineralized water and toluene were added to separate the phases, and the aqueous phase was extracted with toluene. The oil phase was combined and washed sequentially with demineralized water and saturated brine, and after dehydration with anhydrous sodium sulfate, the drying agent was filtered off. The filtrate was concentrated under reduced pressure, and the resulting residue was washed with hexane. The solid was recovered by suction filtration to obtain white crystalline solid phenyl-benzohydroxamate. The yield was 0.53 g (2.5 mmol), and the yield was 31.8%.

[0297] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.76-7.71(m,,2H),7.43-7.25(m,5H),7.09-6.98(m,2H)

[0298] (Synthesis step i-2: Synthesis of O-iminoisourea(i)) A stabilizer was placed in a 50 mL branched flask, and a three-way stopcock connected to a nitrogen line was attached. 0.52 g (2.4 mmol) of phenyl-benzohydroxamate obtained in synthesis i-1, 1.07 g (2.9 mmol) of bis(2,6-diisopropylphenyl)carbodiimide, and 15 mL of THF were added and the mixture was stirred at room temperature. 0.08 g (2.0 mmol) of granular sodium hydroxide was added, and the mixture was reacted at room temperature for 3 hours. The precipitated solid was removed by suction filtration, and the filtrate was concentrated under reduced pressure. The concentrated residue was purified by column chromatography (SiO2 (spherical neutral), hexane:AcOEt = 20:1), and the recovered material was further washed with hexane to obtain white crystalline solid O-iminoisourea(i). The yield was 0.13 g (0.23 mmol), and the yield was 9.3%.

[0299] The structure of the obtained compound was confirmed by NMR spectroscopy. The results are shown below. 1H-NMR(CDCl3) δ(ppm)7.87-7.77(d,2H,J=8.0Hz),7.53-7.46(m,1H),7.45-7.36(m,2H),7.35-7.28(m,1H),7.24-7.16(m,2H),7.02(t,2H,J=8 .4Hz),6.97-6.82(m,4H),6.62-6.47(br,2H),3.55-3.36(br,2H),3.04-2.86(br,2H),1.40-1.21(br,12H),1.08-0.86(br,12H)

[0300] <Investigation of generated radical species> We identified the radical species generated from O-iminoisourea compounds. The response evaluation followed Polymer Journal, vol. 29, No.4, 366-(1997).

[0301] TIFF2026167655000041.tif72170

[0302] A rotor was placed in a small reactor with a side tube, and a three-way stopcock connected to a nitrogen line was attached. The reactor was depressurized, then repressurized with nitrogen to replace the atmosphere inside the container with nitrogen, and 0.019 g (0.05 mmol) of O-iminoisourea(a) obtained above was added to the container through the side tube. Separately, 2,4-diphenyl-4-methyl-1-pentene was placed in a reactor equipped with a three-way stopcock connected to a nitrogen line, the pressure was reduced, the pressure was restored with nitrogen, and then degassed by nitrogen bubbling. From there, the 2,4-diphenyl-4-methyl-1-pentene was added to a reactor containing 0.9 mL (4.0 mmol) of O-iminoisourea(a), and the mixture was heated and stirred in an oil bath for 8 hours to allow it to react. GC-MS analysis of the resulting reaction mixture detected α-ethylstyrene (molecular weight 120). This result indicates that O-iminoisourea(a) generates Me radicals.

[0303] Furthermore, when the O-iminoisourea (b) and (c) obtained above, which have a tBuO group on the imino carbon, were similarly tested, α-ethylstyrene was detected. From this, we confirmed that highly polymerization-reactive Me radicals are generated from O-iminoisourea compounds obtained from t-butylhydroxamate derivatives and carbodiimide derivatives.

[0304] <Solution polymerization evaluation> Solution polymerization of butyl acrylate was evaluated using O-iminoisourea (a), (b), (c), and (f) as thermal polymerization initiators, as shown in the flow chart below.

[0305] TIFF2026167655000042.tif50170

[0306] A rotor was placed in the small reactor, and a three-way stopcock was attached, connected to the nitrogen line. 0.034 g (0.086 mmol) of O-iminoisourea(a) was placed in the reactor, and the reactor was purged with nitrogen by reducing the pressure and then restoring pressure with nitrogen. Decane and butyl acrylate were degassed by reducing the pressure, restoring pressure with nitrogen, and nitrogen bubbling, respectively, and 1 mL of decane (29 vol / O-iminoisourea(a)) and 1.25 mL of butyl acrylate (8.8 mmol, 102 mol / mol-O-iminoisourea(a)) were added to the reactor. The reactor was heated in an oil bath or block heater at 140°C for 15 minutes. 0.2 mL of the reaction solution was taken and dissolved in 1 mL of CDC1, and the 1H NMR was measured. The raw material conversion rate was calculated from the integral values ​​of unreacted butyl acrylate (δ 6.4 ppm, 1H) and butyl acrylate polymer (δ 4.2-3.8 ppm, 2nH) using the following formula. Raw material conversion rate (%) = [(butyl acrylate polymer / 2) / {(butyl acrylate monomer + butyl acrylate polymer) / 2)}] × 100

[0307] For O-iminoisourea (b), (c), (f), (1), and (2), the reaction was similarly evaluated using the same ratio of decane and butyl acrylate as for O-iminoisourea (a) relative to the weight or number of moles of the samples collected.

[0308] [Table 1]

[0309] In Table 1, iminoisourea is a general term for four O-iminoisourea compounds (a), (b), (c), and (f) in the present invention, and two S-iminoisourea compounds (1) and (2) in the comparative example. The general formulas for each iminoisourea shown in Table 1, namely the O-iminoisourea compounds (a), (b), (c), (f) of Examples 1, 2, 3, and 4, and the S-iminoisourea compounds (1) and (2) of Comparative Example 1, are shown below.

[0310] TIFF2026167655000044.tif82170

[0311] Table 1 shows "X-L1", "L2", "L3", and "R 4、5 " are "L1", "L2", "L3", and "R" respectively when n=1 in equation (I). 4、5 " In Table 1, "OtBu" represents an oxygen-t-butyl group, "S-tol" represents a sulfur-4-methylphenyl group, and "S-Me" represents a sulfur-methyl group. "Ph" represents a phenyl group, "py" represents a 4-pyridyl group, "Me" represents a methyl group, "H" represents a hydrogen atom, "iPr" represents an isopropyl group, "c-hex" represents a cyclohexyl group, and "iPr2Ph" represents an isopropyl-2phenyl group. Furthermore, "butyl acrylate / O-iminoisourea" is the ratio of butyl acrylate (mol) to the amount of O-iminoisourea (mol) in the above solution polymerization reaction. "Solvent (decane)" refers to the amount of n-decane used as the reaction solvent. The "butyl acrylate conversion rate" is the raw material conversion rate mentioned above.

[0312] (Consideration) In Examples (a), (b), (c), and (f) of the alkoxy-substituted (oxygen)-iminoisourea, the raw material conversion rate was 93% or higher, whereas in Comparative Examples 1 and 2, the raw material conversion rates (butyl acrylate conversion rate) were 60.0% and 79.6%, respectively. Furthermore, in the blank without a thermal polymerization initiator, no polymer was formed at all. From this, it was confirmed that the alkoxy-substituted O-iminoisourea in the example acts as a thermal polymerization initiator and exhibits higher reactivity than the comparative example.

[0313] Based on the results of the above examples and comparative examples, as well as the test results conducted by the inventors to date, it has been found that the O-iminoisourea compound represented by formula (I) is stable at room temperature and generates radicals upon heating, exhibiting polymerization activity, thus functioning as a thermal polymerization initiator. In particular, it was confirmed that L1 in formula (I) decomposes sequentially, like a t-butyl group, to generate Me radicals, and polymerization-inactive species such as N radicals are converted into polymerization-active species, resulting in higher reactivity. Furthermore, it was confirmed that these Me radicals are more active than S radicals. In addition, it was confirmed that the steric size of the radicals is smaller due to the sequential decomposition, resulting in excellent mobility.

[0314] TIFF2026167655000045.tif37170

[0315] Therefore, in the O-iminoisourea compound represented by formula (I), if L1 is t-butyl, 2-methyl-2-butyl group, 3-methyl-3-pentyl group, 1,1-diphenylethyl group, or acetyl group, it is thought that Me radicals are generated by the sequential decomposition of N radicals, and thus similar mechanisms of action and effects can be obtained. In this case, substituents other than L1 are also considered. 2、 L 3、 It is believed that any substituent for R4 and R5 can achieve the same mechanism of action and effect, unless there is a specific reason to hinder the effect. Furthermore, since methoxy radicals, ethoxy radicals, and phenoxy radical-substituted phenyls are thought to act similarly to Me radicals, it is believed that similar mechanisms of action and effects can be obtained even if L1 is methyl, ethyl, phenyl, or a substituted phenyl. In this case as well, substituents other than L1 are also considered. 2、 L 3、 It is believed that any substituent for R4 and R5 can achieve the same mechanism of action and effect, unless there is a specific reason to hinder the effect.

Claims

1. O-iminoisourea compounds represented by the following general formula (I) (excluding O-iminoisourea compounds represented by the following structural formula (I)-A). (In equation (I), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ may each have one or more O, N, S, Si or halogen atoms.)

2. O-iminoisourea compound salts represented by the following general formula (II). (In equation (II), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ It may have one or more O, N, S, Si, or halogen atoms. Y is hydrogen, or C １ ~C １０ It is an alkyl group. m+ and m- represent electric charge, where m is an integer from 1 to 4. X ｍ－ (This refers to one or more ions selected from the group consisting of halide ions, sulfate anions, bisulfate anions, tetrafluoroborate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, and aryl carboxylate anions, provided that the total valency is -m.)

3. An O-iminoisourea complex represented by the following general formula (III). (In equation (III), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ It may have one or more O, N, S, Si, or halogen atoms. Z ｐ These are Lewis acidic compounds, such as boron halides, aluminum halides, and C １ ~C ４ Tri(alkyloxy)boric acid, C ６ ~C １０ It is one or more substances selected from the group consisting of tri(aryloxy)boric acid, zinc chloride, and cuprous chloride. p represents the number of Z, and is an integer less than or equal to n.

4. L in (I), (II), and (III) of the above formulas １ , L ２ , L ３、 R ４ and R ５ The O-iminoisourea compound according to claim 1, the O-iminoisourea compound salt according to claim 2, or the O-iminoisourea complex according to claim 3, wherein the number of carbon atoms in each organic group is 30 or less.

5. The O-iminoisourea compound, O-iminoisourea compound salt, or O-iminoisourea complex according to claim 4, wherein n = 1 in formulas (I), (II), and (III).

6. In the above formulas (I), (II), and (III), L １ The O-iminoisourea compound, O-iminoisourea compound salt, or O-iminoisourea complex according to claim 5, wherein the number of carbon atoms is 10 or less.

7. In the above formulas (I), (II), and (III), L １ The O-iminoisourea compound, O-iminoisourea compound salt, or O-iminoisourea complex according to claim 5, wherein the group is a butyl group.

8. A thermal polymerization initiator comprising one or more of the following: an O-iminoisourea compound represented by the following general formula (I), an O-iminoisourea compound salt represented by the following general formula (II), and an O-iminoisourea complex represented by the following general formula (III). (In equation (I), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ (It may have one or more O, N, S, Si, or halogen atoms.) (In equation (II), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ It may have one or more O, N, S, Si, or halogen atoms. Y is hydrogen, or C １ ~C １０ It is an alkyl group. m+ and m- represent electric charge, where m is an integer from 1 to 4. X ｍ－ (This refers to one or more ions selected from the group consisting of halide ions, sulfate anions, bisulfate anions, tetrafluoroborate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, and aryl carboxylate anions, provided that the total valency is -m.) (In equation (III), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ may each have one or more O, N, S, Si or halogen atoms. Z ｐ These are Lewis acidic compounds, such as boron halides, aluminum halides, and C １ ~C ４ Tri(alkyloxy)boric acid, C ６ ~C １０ It is one or more substances selected from the group consisting of tri(aryloxy)boric acid, zinc chloride, and cuprous chloride. p represents the number of Z, and is an integer less than or equal to n.

9. A polymerizable composition comprising the thermal polymerization initiator described in claim 8 and a polymerizable compound.

10. The polymerizable composition according to claim 9, wherein the polymerizable compound comprises an acrylate compound, a methacrylate compound, or both.

11. A cured product of the polymerizable composition according to claim 10.

12. A method for producing a hydroxamate derivative which is an intermediate in the production of an O-iminoisourea compound represented by the general formula (I) described in claim 1 (including compounds excluded in claim 1), A method for producing a hydroxamate derivative, comprising: reacting a compound represented by compound (1) shown by the following general formula with a silylating agent shown by the following formula in the presence of a base to synthesize an oxime chloride silyl ether derivative of the following general formula (2); and reacting the oxime chloride silyl ether derivative with a metal alkoxide shown by the following general formula (3) to synthesize a hydroxamate derivative shown by the following general formula (4). (L in Formulas (1) to (4) １ and L ２ are the same as L in the aforementioned Formula (I) １ and L ２ . The leaving group in the formula representing the silylating agent is an anionic leaving group. In the formula representing the silylating agent and Formula (2), R ａ , R ｂ and R ｃ are each independently a C １ to C １０ alkyl group, or a C １ to C １０ aryl group which may be substituted with an alkyl group of C ６ to C ２０ .)

13. A method for producing an O-iminoisourea compound represented by the general formula (I) described in claim 1 (including compounds excluded in claim 1), The hydroxamate derivative represented by general formula (4) obtained by the manufacturing method according to claim 12 is reacted with a carbodiimide derivative to obtain L in general formula (I). ３ A method for producing O-iminoisourea compounds, comprising synthesizing O-iminoisourea compounds in which hydrogen is present.

14. An O-iminoisourea compound represented by the following general formula (I), and an acidic compound or C represented by the following formula. １ ~C １０ A method for producing an O-iminoisourea compound salt, comprising reacting an alkyl halide compound Y-X with the O-iminoisourea compound salt represented by the following general formula (II). (In equation (I), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ (It may have one or more O, N, S, Si, or halogen atoms.) (In equation (II), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ It may have one or more O, N, S, Si, or halogen atoms. Y is hydrogen, or C １ ~C １０ It is an alkyl group. m+ and m- represent electric charge, where m is an integer from 1 to 4. X ｍ－ (This refers to one or more ions selected from the group consisting of halide ions, sulfate anions, bisulfate anions, tetrafluoroborate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, and aryl carboxylate anions, provided that the total valency is -m.)

15. A method for producing an O-iminoisourea complex, comprising reacting an O-iminoisourea compound represented by the following general formula (I) with a Lewis acid compound pZ represented by the following formula to synthesize an O-iminoisourea complex represented by the following general formula (III). (In equation (I), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ (It may have one or more O, N, S, Si, or halogen atoms.) (In equation (III), n is an integer from 1 to 4, R ４ , R ５ It is a monovalent organic group. If n=1, L １、 L ２ and L ３ It is a monovalent organic group, If n is between 2 and 4, L １ ~L ３ One of them is an n-valent organic group, and the others are monovalent organic groups. L １ , L ２ , L ３、 R ４ and R ５ It may have one or more O, N, S, Si, or halogen atoms. Z ｐ These are Lewis acidic compounds, such as boron halides, aluminum halides, and C １ ~C ４ Tri(alkyloxy)boric acid, C ６ ~C １０ It is one or more substances selected from the group consisting of tri(aryloxy)boric acid, zinc chloride, and cuprous chloride. p represents the number of Z, and is an integer less than or equal to n.

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