Carbamoyloxime compound, and polymerization initiator and polymerizable composition containing said compound

Abstract

The present invention addresses the problem of providing a compound having high photobase generation efficiency. The present invention is a carbamoyl oxime compound represented by general formula (I). In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R1 0 each independently denote a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl oxime group, or the like. At least one of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R1 0 is a carbamoyl oxime group. The carbamoyl oxime group includes, in the structure thereof, a ring which comprises hydrogen atoms, nitrogen atoms and carbon atoms and in which the number of carbon atoms is 2-10 or a ring which comprises hydrogen atoms, oxygen atoms, nitrogen atoms and carbon atoms and in which the number of carbon atoms is 2-10.

Description

[Technical field]

[0001] The present invention relates to carbamoyl oxime compounds. [Background technology]

[0002] In general, polymerizable compositions such as photosensitive resin compositions are prepared by adding a photopolymerization initiator to a polymerizable compound such as a photosensitive resin, and can be polymerized and cured or developed by irradiation with energy rays (light). Therefore, they are used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, and the like.

[0003] Photopolymerization initiators are classified into photoradical generators, photoacid generators, and photobase generators according to the difference in the active species generated by irradiation with energy rays (light). Photoradical generators have advantages such as a fast curing speed and no remaining active species after curing, but have a disadvantage that a layer that blocks oxygen must be provided when curing a thin film because curing is inhibited by oxygen. Photoacid generators have the advantage of not being inhibited by oxygen, but have disadvantages such as corrosion of metal substrates and denaturation of resins after curing due to remaining acids of active species. Photobase generators have attracted attention because they are less likely to cause problems such as curing inhibition by oxygen and corrosion by remaining active species, but generally have a problem of low sensitivity (low curability) compared to photoacid generators. Photobase generators are described in, for example, Patent Documents 1 and 2. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] US9594302 [Patent Document 2] JP 2013-163670 A Summary of the Invention

[0005] However, conventional photobase generators have low base generation efficiency and insufficient sensitivity. Therefore, an object of the present invention is to provide a compound having high photobase generation efficiency.

[0006] The present inventors have conducted extensive research and found that a compound having a specific structure has high photobase generation efficiency and is useful as a polymerization initiator. That is, the present invention is a carbamoyl oxime compound represented by the following general formula (I).

[0007] [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR 11 , -COOR 11 , -CO-R 11 , -SR 11 a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II): R 11 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and when R 11 When multiple are present, they may be the same or different, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 12 , -COOR 12 , -CO-R 12 or -SR 12 may be a group having 1 to 20 carbon atoms substituted with R 12 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and if R 12 When multiple are present, they may be the same or different, <Group A> is -O-, -CO-, -COO-, -NR 13 -, -NR 13 CO- and -S-, R 13 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 13 When multiple are present, they may be the same or different, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 may each independently be linked to each other to form a ring having 3 to 10 carbon atoms and composed of hydrogen atoms and carbon atoms, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R10 At least one of the groups is a group represented by the following general formula (II): When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different.

[0008] [ka] (In the formula, R 20 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, X 1 -NR 21 R 22 or a group represented by the following general formula (a) or the following general formula (b): R 21 and R 22 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, R 20 , R 21 and R 22 is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 23 , -COOR 23 , -CO-R 23 or -SR 23 may be a group having 1 to 20 carbon atoms substituted with R 23 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and 23 When multiple are present, they may be the same or different, <Group B> is -O-, -CO-, -COO-, -NR 24 -, -NR24 CO- and -S-, R 24 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 24 When multiple are present, they may be the same or different, R 21 and R 22 may be linked together to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, n represents 0 or 1; * represents a bond.)

[0009] [ka] (In the formula, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 41 , -COOR 41 , -CO-R 41 or -SR 41 may be a group having 1 to 20 carbon atoms substituted with R 41 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R41 When multiple are present, they may be the same or different, <Group C> is -O-, -CO-, -COO-, -NR 42 -, -NR 42 CO- and -S-, R 42 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 42 When multiple are present, they may be the same or different, R 31 and R 32 , R 33 and R 34 , R 35 and R 36 , R 37 and R 38 , and R 39 and R 40 may each independently link to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, * represents a bond.) DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in detail below. The carbamoyl oxime compound of the present invention is represented by the above general formula (I). The carbamoyl oxime compound represented by the above general formula (I) has geometric isomers due to the double bond of the oxime, but these are not distinguished from each other. In other words, in this specification, the carbamoyl oxime compound represented by the above general formula (I), as well as the compounds and example compounds which are preferred forms of the compound described later, represent a mixture of isomers or either one of them, and are not limited to the isomers of the structures shown. Hereinafter, the carbamoyloxime compound represented by the above general formula (I) may be simply referred to as "the compound represented by general formula (I)" or "the compound of the present invention".

[0011] Examples of the halogen atom in the general formula (I), the general formula (II), the general formula (a) and the general formula (b) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0012] Examples of the hydrocarbon group having 1 to 20 carbon atoms in the above general formula (I), general formula (II), general formula (a) and general formula (b) include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0013] Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, amyl group, isoamyl group, t-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, t-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and icosyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; and cycloalkylalkyl groups such as cyclohexylmethyl group, as well as unsaturated aliphatic hydrocarbon groups in which the carbon-carbon single bond of these groups is replaced with a carbon-carbon double bond or a carbon-carbon triple bond.

[0014] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a benzyl group, a naphthyl group, a phenanthryl group, a pyrenyl group, and a biphenyl group.

[0015] R 1 ~R 11 In the hydrocarbon group represented by the formula: 12 , -COOR 12 , -CO-R 12 or -SR 12The C1-20 group substituted with is preferably one in which one or more hydrogen atoms in the C1-20 hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 12 , -COOR 12 , -CO-R 12 or -SR 12 and the total number of carbon atoms is 1 to 20. 12 The group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, as represented by the formula (I), includes a group having a structure in which one or more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and having a total of 1 to 20 carbon atoms.

[0016] R 1 ~R 12 The C1-20 group in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the above <Group A>, is preferably a group in which one or more of the methylene groups in the C1-20 hydrocarbon group are substituted with -O-, -CO-, -COO-, -NR 13 -, -NR 13 Examples of the group include a structure substituted with -CO- or -S- and having a total of 1 to 20 carbon atoms.

[0017] R 20 ~R 22 In the hydrocarbon group represented by the formula: 23 , -COOR 23 , -CO-R 23 or -SR 23 The C1-20 group substituted with is preferably one in which one or more hydrogen atoms in the C1-20 hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 23 , -COOR 23 , -CO-R 23 or -SR 23 and the total number of carbon atoms is 1 to 20. 23The group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, as represented by the formula (I), includes a group having a structure in which one or more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and having a total of 1 to 20 carbon atoms.

[0018] R 20 ~R 23 The C1-20 group in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the above <Group B>, is preferably a group in which one or more of the methylene groups in the above C1-20 hydrocarbon group are substituted with -O-, -CO-, -COO-, -NR 24 -, -NR 24 Examples of the group include a structure substituted with -CO- or -S- and having a total of 1 to 20 carbon atoms.

[0019] R 31 ~R 40 In the hydrocarbon group represented by the formula: 41 , -COOR 41 , -CO-R 41 or -SR 41 The C1-20 group substituted with is preferably one in which one or more hydrogen atoms in the C1-20 hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 41 , -COOR 41 , -CO-R 41 or -SR 41 and the total number of carbon atoms is 1 to 20.

[0020] R 31 ~R 40 The C1-20 group in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the above <Group C>, is preferably a group in which one or more of the methylene groups in the above C1-20 hydrocarbon group are substituted with -O-, -CO-, -COO-, -NR 42 -, -NR 42Examples of the group include a structure substituted with -CO- or -S- and having a total of 1 to 20 carbon atoms.

[0021] Examples of the heterocycle-containing group having 2 to 20 carbon atoms in the above general formula (I) include groups containing a tetrahydrofuranyl group, a dioxolanyl group, a tetrahydropyranyl group, a morpholyl group, a furanyl group, a thiophenyl group, a methylthiophenyl group, a hexylthiophenyl group, a benzothiophenyl group, a pyrrolyl group, a pyrrolidinyl group, an imidazolyl group, an imidazolinyl group, an imidazolidinyl group, a pyrazolinyl group, a pyrazolidinyl group, a piperidinyl group, and a piperazinyl group.

[0022] The heterocyclic ring-containing group having 2 to 20 carbon atoms is preferably a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 50 , -COOR 50 , -CO-R 50 or -SR 50 and the like, and may have a substituent such as -O-, -CO-, -COO-, -NR 51 -, -NR 51 It may contain structures such as -CO- or -S-. Here, R 50 and R 51 R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 50 and R 51 The hydrocarbon group having 1 to 20 carbon atoms represented by the following formula is the same as the hydrocarbon group having 1 to 20 carbon atoms in the above general formula (I), the above general formula (II), the above general formula (a) and the above general formula (b).

[0023] R in the above general formula (I) 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R9 and R 10 Examples of the ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms formed by linking together include a benzene ring, a cyclohexene ring, a cyclohexane ring, a cyclopentadiene ring, a cyclopentane ring, etc. Furthermore, these rings may have a substituent, and in this case, examples of the substituent include the substituents that may be possessed by the heterocycle-containing group having 2 to 20 carbon atoms.

[0024] R in the above general formula (II), the above general formula (a) and the above general formula (b) 21 and R 22 , R 31 and R 32 , R 33 and R 34 , R 35 and R 36 , R 37 and R 38 , and R 39 and R 40 Examples of the ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms formed by linking together include a pyrrole ring, pyrrolidine ring, imidazole ring, imidazolidine ring, imidazoline ring, pyrazole ring, pyrazolidine ring, piperidine ring, piperazine ring, etc. These rings may have a substituent, and examples of the substituent in this case include the substituents that may be carried by the heterocycle-containing group having 2 to 20 carbon atoms.

[0025] R in the above general formula (II), the above general formula (a) and the above general formula (b) 21 and R 22 , R 31 and R 32 , R 33 and R 34 , R 35 and R 36 , R 37 and R 38 , and R 39 and R 40Examples of the ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms formed by linking together include a morpholine ring, an oxazole ring, an oxazoline ring, an oxadiazole ring, etc. These rings may have a substituent, and in this case, examples of the substituent include the substituents that may be possessed by the heterocycle-containing group having 2 to 20 carbon atoms.

[0026] In the present invention, R in the general formula (I) is preferred because it is easy to synthesize, has high storage stability, and has high base generation efficiency. 3 and R 8 Among these, a carbamoyloxime compound in which either or both of the above is a group represented by the above general formula (II) is preferred.

[0027] R in general formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Among these, at least one other than the group represented by the general formula (II) is -CO-R 11 The carbamoyl oxime compound represented by the formula R is preferred because the resulting polymerizable composition can be cured with a low exposure dose. 8 is a group represented by the above general formula (II), and R 3 Ga-CO-R 11 The carbamoyl oxime compound represented by the formula R is preferred because it is easy to synthesize and has high storage stability. 11 is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms, since the resulting polymerizable composition can be cured with a low exposure dose, and is more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms or a heterocyclic ring-containing group having 2 to 10 carbon atoms. 11 is preferably a phenyl group, a tolyl group, a mesityl group, a benzofuranyl group or a thienyl group.

[0028] In addition, R in the general formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Among these, carbamoyloxime compounds in which at least one group other than the group represented by the general formula (II) is a nitro group are also preferred because the resulting polymerizable composition can be cured with a low exposure dose. 8 is a group represented by the above general formula (II), and R 3 Carbamoyl oxime compounds in which is a nitro group are preferred.

[0029] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, -CO-R 11 A nitro group or a carbamoyloxime compound represented by the above general formula (II) is preferred because of its high base generation efficiency.

[0030] In addition, X in the general formula (II) 1 Ga-NR 21 R 22 Carbamoyl oxime compounds represented by the formula R are preferred because of their high base generation efficiency. 21 and R 22 are more preferably linked to each other to form a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms. In particular, R 21 and R 22 are preferably linked to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms and carbon atoms, and more preferably form a piperidine ring or a pyrrolidine ring.

[0031] In addition, X in the general formula (II) 1 Ga-NR 21 R 22 In the carbamoyl oxime compound, R 21 is a hydrogen atom, and R 22 is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 21 and R 22 are each preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, since this results in high base generation efficiency.

[0032] Carbamoyloxime compounds in which n is 0 in the above general formula (II) are preferred because they have high thermal stability. A carbamoyloxime compound in which n is 1 in the above general formula (II) is preferred because the resulting polymerizable composition is cured at a low exposure dose.

[0033] Specific examples of the carbamoyloxime compound represented by the above general formula (I) include compounds represented by the following chemical formulas (1) to (62). However, the present invention is not limited to the following compounds.

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] The method for producing the carbamoyl oxime compound of the present invention represented by the above general formula (I) is not particularly limited. For example, 8 is a group represented by general formula (II), and X 1 Ga-NR 21 R 22 When n=0, it can be produced by the following method according to the following reaction scheme 1. That is, a known ketone compound is reacted with hydroxylamine hydrochloride in the presence of a base such as pyridine to obtain an oxime compound, which is then reacted with 4-nitrophenyl chloroformate and then with an amine to obtain the carbamoyl oxime compound of the present invention.

[0044] [ka] (In the formula, R 1 ~R 10 , R 20 ~R 22 is the same as in general formula (I) above.

[0045] The above reaction formula 1 is X 1 Ga-NR 21 R22 However, by changing the amine used, 1 is a group represented by the above general formula (a) or (b). In addition, the above reaction formula 1 is represented by the formula (I) 8 is a group represented by general formula (II), but R 8 By using a ketone compound with a ketone group introduced at any position other than R 8 It is also possible to obtain a compound having a group represented by general formula (II) introduced at a position other than the position. The oxime compound can also be produced by the method described in Japanese Patent No. 4223071.

[0046] INDUSTRIAL APPLICABILITY The carbamoyloxime compound of the present invention efficiently generates bases and radicals upon irradiation with light such as ultraviolet light or heating, and is therefore useful as a latent base generator and a polymerization initiator, and is particularly useful as a latent base generator.

[0047] The latent base generator of the present invention means a composition containing a compound having a function of efficiently generating a base when irradiated with light such as ultraviolet light, and examples of uses of the latent base generator include a pH adjuster and a catalyst that utilizes a base.

[0048] Furthermore, the carbamoyl oxime compound of the present invention is useful as a photobase generator and a photoradical polymerization initiator since it has high efficiency of generating a base and a radical by light irradiation among the above-mentioned polymerization initiators, and is particularly useful as a photobase generator since it has extremely high efficiency of generating a base.

[0049] The polymerization initiator of the present invention contains at least one carbamoyl oxime compound represented by the above general formula (I). The polymerization initiator that can be used in combination with the carbamoyl oxime compound represented by the above general formula (I) is not particularly limited, and examples thereof include conventionally known photobase generators and photoradical polymerization initiators.

[0050] The content of the compound represented by the general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, and more preferably 50 to 100% by mass, since the resulting polymerizable composition is cured with a low exposure dose.

[0051] The polymerizable composition of the present invention contains a polymerization initiator (A) containing at least one carbamoyloxime compound represented by the above general formula (I), and a polymerizable compound (B). The content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the polymerizable compound (B), since the resulting polymerizable composition is cured at a low exposure dose. The content of the polymerization initiator (A) of 1 part by mass or more is preferable because it is easy to prevent curing failure due to insufficient curing sensitivity, and the content of 20 parts by mass or less is preferable because it is possible to suppress volatile matter during light irradiation or heating.

[0052] The polymerizable compound (B) used in the present invention includes a compound having an anionically polymerizable functional group, a compound cured by a reaction in which a base acts as a catalyst or a reaction in which a base is added, and a radically polymerizable compound. A photosensitive resin that is polymerized and cured by irradiation with energy rays such as ultraviolet rays, or a curable resin that has a low curing temperature is preferable because the obtained polymerizable composition is cured with a low exposure dose. The anionically polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator by active energy rays such as ultraviolet rays, and examples thereof include an epoxy group, an episulfide group, a cyclic monomer (σ-valerolactone, ε-caprolactam), a malonic acid ester, etc. Examples of reactions in which a base acts as a catalyst or in which a base is added include the urethane bond formation reaction between isocyanate and alcohol, the addition reaction of an epoxy resin and a compound containing a hydroxyl group, the addition reaction of an epoxy resin and a compound containing a carboxylic acid group, the addition reaction of an epoxy resin and a thiol compound, the Michael addition reaction of (meth)acrylic groups, the dehydration condensation reaction of polyamic acid, and the hydrolysis and polycondensation reaction of alkoxysilanes.

[0053] Examples of compounds having an anionically polymerizable functional group include epoxy resins, oxetane resins, episulfide resins, cyclic amides (lactam compounds), cyclic esters (lactone compounds), cyclic carbonate compounds, and malonic acid esters. Examples of compounds that harden by a reaction catalyzed by a base or a reaction in which a base is added include polyamide resins (polyimide formation reaction by dehydration cyclization), epoxy-hydroxyl group systems (ring-opening addition reaction), epoxy-carboxylic acid systems (ring-opening addition reaction), epoxy-thiol systems (ring-opening addition reaction), epoxy-acid anhydride systems (ring-opening polycondensation), cyanate esters (triazine cyclization reaction), cyanate ester-epoxy systems (cyclization reaction), cyanate ester-maleimide systems (crosslinking copolymerization), oxetane-hydroxyl group systems (ring-opening addition reaction), oxetane-carboxylic acid systems (ring-opening addition reaction), oxetane-thiol systems (ring-opening addition reaction), oxetane-acid anhydride systems (ring-opening polycondensation), oxetane-hydroxyl group systems (ring-opening addition reaction), oxetane-carboxylic acid systems (ring-opening addition reaction), oxetane-thiol systems (ring-opening addition reaction), oxetane-acid anhydride systems (ring-opening polycondensation), oxetane-hydroxyl group systems (ring-opening addition reaction), oxetane-carboxylic acid systems (ring-opening addition reaction), oxetane-acid anhydride systems (ring-opening polycondensation), oxetane-hydroxyl group systems (ring-opening addition reaction ... Examples of such compounds include bisulfide-hydroxyl group (ring-opening addition reaction), episulfide-carboxylic acid group (ring-opening addition reaction), episulfide-thiol group (ring-opening addition reaction), episulfide-acid anhydride group (ring-opening polycondensation), acrylic-thiol group (Michael addition reaction), methacrylic-thiol group (Michael addition reaction), acrylic-amine group (Michael addition reaction), methacrylic-amine group (Michael addition reaction), carboxylic acid-hydroxyl group (polyesterification reaction), carboxylic acid-amine group (polyamidation reaction), isocyanate-hydroxyl group (polyurethane reaction), isocyanate-thiol group (polythiourethane reaction), and alkoxysilane group (hydrolysis and polycondensation). Compounds that polymerize by radicals include ethylenically unsaturated compounds. It is preferable to use compounds that polymerize by radical polymerization because of their high reactivity. These resins may be used alone or in combination of two or more types. Preferred combinations include a combination of an epoxy resin and a phenol resin, which allows the reaction to proceed quickly and provides good adhesion; a combination of an epoxy resin and a thiol compound, which provides excellent low-temperature curing properties; and a combination of an ethylenically unsaturated compound and a thiol compound, which provides high reactivity.

[0054] The epoxy resin may have an epoxy group, but does not include the carbamoyloxime compound of the present invention. Examples of epoxy resins include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(ortho-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidene bis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, ortho-cresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenol. Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, triglyceride, etc. glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids, such as merocalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; epoxy compounds having a glycidylamino group, such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl orthotoluidine;Examples of epoxy resins include cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymers, and epoxidized styrene-butadiene copolymers; and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be internally crosslinked with a prepolymer of terminal isocyanate or may be polymerized with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate, etc.); Among the above epoxy resins, those having a glycidyl group are preferred, and those having di- or higher-functional glycidyl groups are more preferred, in terms of excellent curability of the resulting polymerizable composition.

[0055] The phenolic resin may have a phenolic hydroxyl group, but does not include the carbamoyl oxime compound and the epoxy resin. As the phenolic resin, a phenolic resin having two or more hydroxyl groups in one molecule is preferred because the resulting polymerizable composition has excellent curability, and generally known phenolic resins can be used. Examples of phenolic resins include bisphenol A type phenolic resins, bisphenol E type phenolic resins, bisphenol F type phenolic resins, bisphenol S type phenolic resins, phenol novolac resins, bisphenol A novolac type phenolic resins, glycidyl ester type phenolic resins, aralkyl novolac type phenolic resins, biphenyl aralkyl type phenolic resins, cresol novolac type phenolic resins, multifunctional phenolic resins, naphthol resins, naphthol novolac resins, multifunctional naphthol resins, anthracene type phenolic resins, naphthalene skeleton modified novolac type phenolic resins, phenol aralkyl type phenolic resins, naphthol aralkyl type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic phenolic resins, polyol type phenolic resins, phosphorus-containing phenolic resins, polymerizable unsaturated hydrocarbon group-containing phenolic resins, and hydroxyl group-containing silicone resins, but are not particularly limited. These phenolic resins can be used alone or in combination of two or more.

[0056] The thiol compound may have a thiol group, but excludes the carbamoyloxime compounds, epoxy resins, and phenolic resins. Among the thiol compounds, those having two or more thiol groups in one molecule are preferred because the resulting polymerizable composition has excellent curability. Specific preferred examples of the thiol compound include bis(2-mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol, 1,1,3,3-tetrakis(mercaptomethyl) Examples of the mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane include 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, and trimethylolpropane trismercaptopropionate, and more preferably, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol thiol, bis(2-mercaptoethyl)sulfide, 2,5-bis(2-mercaptomethyl)-1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,3-bis(mercaptomethyl)benzene, pentaerythritol tetrakismercaptopropionate, and pentaerythritol tetrakisthioglycolate. Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythrithiol, bis(2-mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. The thiol compounds can be used alone or in combination of two or more.

[0057] Examples of the polyamide resin include resins made from acid dianhydrides such as ethylene tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2,3,3-biphenyl tetracarboxylic anhydride, and 1,4,5,8-naphthalene tetracarboxylic dianhydride, and diamines such as (o-, m-, or p-)phenylenediamine, (3,3'- or 4,4'-)diaminodiphenyl ether, diaminobenzophenone, and (3,3'- or 4,4'-)diaminodiphenylmethane.

[0058] Examples of the polyurethane resin include resins made from polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate, and polyols (polyfunctional alcohols) such as polyether polyol, polyester polyol, and polycarbonate polyol. Examples of the nylon resin include resins made from cyclic monomers such as ε-caprolactam and lauryllactam. Examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone.

[0059] The ethylenically unsaturated compound may have an ethylenically unsaturated bond, but does not include the carbamoyl oxime compound, the epoxy resin, the phenol resin, and the thiol compound. Examples of the ethylenically unsaturated compound include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono[2-(meth)acryloyloxyethyl] succinate, and phthalic acid. mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as mono[2-(meth)acryloyloxyethyl] carboxylate and ω-carboxypolycaprolactone mono(meth)acrylate; unsaturated polybasic acids, such as hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, or polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups;2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, Dimethylaminomethyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Aminopropyl (meth)acrylate, Dimethylaminopropyl (meth)acrylate, Ethoxyethyl (meth)acrylate, Poly(ethoxy)ethyl (meth)acrylate, Butoxyethoxyethyl (meth)acrylate, Ethylhexyl (meth)acrylate, Phenoxyethyl (meth)acrylate, Tetrahydrofuryl (meth)acrylate, Vinyl (meth)acrylate, Allyl (meth)acrylate, Vinyl (meth)acrylate , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate )acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester(meth)acrylate oligomers, and other unsaturated monobasic acids and esters of polyhydric alcohols or polyhydric phenols; metal salts of unsaturated polybasic acids, such as zinc (meth)acrylate and magnesium (meth)acrylate;Acid anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, and methylhimic anhydride; (meth)acrylamide, methylene bis(meth)acrylamide Amides of unsaturated monobasic acids and polyamines such as diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl(meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chloro unsaturated aromatic compounds such as styrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane;Examples of the vinyl urethane compounds include vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds; The ethylenically unsaturated compounds can be used alone or in combination of two or more.

[0060] As the ethylenically unsaturated compound, commercially available products can be used, such as Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (all manufactured by Nippon Kayaku Co., Ltd.); Aronix M-215, M-350 (all manufactured by Toagosei Co., Ltd.); NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (all manufactured by Showa Denko Co., Ltd.); and the like.

[0061] The content of the polymerizable composition (B) may be an appropriate amount depending on the purpose of use, but in order to prevent poor curing, it is preferable to include it in an amount of 50 parts by mass or more of the solid content (all components other than the solvent) in the polymerizable composition, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more.

[0062] The polymerizable composition of the present invention may contain, as optional components, additives such as inorganic compounds, coloring materials, latent epoxy curing agents, chain transfer agents, sensitizers, and solvents.

[0063] Examples of the inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder (particularly glass frit), mica, talc, kaolin, ferrocyanides, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. These inorganic compounds are used, for example, as fillers, antireflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink developers, etc.

[0064] The coloring material includes pigments, dyes, natural dyes, etc. These coloring materials can be used alone or in combination of two or more kinds.

[0065] Examples of the pigments include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthranthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid, metal complex compounds of azo dyes and cyanine dyes, lake pigments, furnace and chalcogenides. carbon black obtained by a tunnel method or a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin; the above carbon black previously dispersed in a solvent with a resin to adsorb 20 to 200 mg / g of resin; the above carbon black subjected to an acidic or alkaline surface treatment; carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less; 2Carbon black having a weight of 9 mg or more per unit weight; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, synthetic iron black, amber, and other organic or inorganic pigments can be used. These pigments can be used alone or in combination.

[0066] As the pigment, commercially available pigments can be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 198, 199, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 24 4, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1 ,3,12,13,14,16,17,20,24,55,60,73,81,83,86,93,95,97,98,100,109,110,113,114,117,120,125,126,127,129,137,138,139,147,148,150,151,152,153,154,166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

[0067] Examples of the dye include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and these dyes may be used in combination.

[0068] Examples of the latent epoxy curing agent include dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenyl sulfone, boron trifluoride amine complex salts, imidazoles, guanamines, imidazoles, ureas, and melamine.

[0069] As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercapto) disulfide compounds obtained by oxidizing the mercapto compounds; iodized alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid; trimethylolpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, and Tandiol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, and the following compound No.Examples of the thiol compounds include aliphatic polyfunctional thiol compounds such as C1, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, and Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko Co., Ltd.

[0070] [ka]

[0071] The above-mentioned solvent is usually a solvent capable of dissolving or dispersing each of the above-mentioned components (polymerization initiator (A) and polymerizable compound (B), etc.), for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc.; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid, etc. ester-based solvents such as isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; lactone-based solvents such as γ-caprolactone, δ-caprolactone, and γ-butyrolactone; cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate Ether ester solvents such as propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.) ) and other paraffin-based solvents; halogenated aliphatic hydrocarbon-based solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, and other halogenated aromatic hydrocarbon-based solvents; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; water, and the like can be used, and these solvents can be used alone or as a mixed solvent of two or more kinds. Among these, from the viewpoints of alkaline developability, patterning ability, film-forming ability, and solubility, ketones or ether ester solvents, in particular, propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as "PGMEA") or cyclohexanone are preferably used. In the polymerizable composition of the present invention, the content of the solvent is not particularly limited as long as each component is uniformly dispersed or dissolved and the polymerizable composition of the present invention exhibits a liquid or paste state suitable for each application. However, it is usually preferable to contain the solvent in a range such that the amount of solids in the polymerizable composition of the present invention (all components other than the solvent) is 10 to 90 mass %, since a uniform cured product can be obtained.

[0072] In addition, the polymerizable composition of the present invention can improve the properties of the cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, and phenoxy resin. When the organic polymer is used, the content thereof is preferably 10 to 500 parts by mass per 100 parts by mass of the polymerizable compound (B) since the resulting polymerizable composition has excellent curability.

[0073] The polymerizable composition of the present invention may further contain a surfactant, a silane coupling agent, a melamine compound, or the like.

[0074] Examples of the surfactant that can be used include fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; cationic surfactants such as higher amine halogen acid salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides; amphoteric surfactants; and silicone-based surfactants, which may be used in combination.

[0075] As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, silane coupling agents having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403, are preferably used.

[0076] Examples of the melamine compound include nitrogen compounds such as (poly)methylol melamine, (poly)methylol glycol uril, (poly)methylol benzoguanamine, and (poly)methylol urea, in which all or a part (at least two) of the active methylol groups (CHOH groups) are alkyl-etherified. Here, the alkyl group constituting the alkyl ether may be a methyl group, an ethyl group, or a butyl group, which may be the same as or different from each other. Furthermore, the methylol group that is not alkyl etherified may be self-condensed in one molecule, or may be condensed between two molecules to form an oligomer component. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. can be used. Among these, alkyl-etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred from the viewpoints of solubility in a solvent and resistance to crystallization from the polymerizable composition.

[0077] In the polymerizable composition of the present invention, the content of optional components other than the polymerization initiator (A) and the polymerizable compound (B) (excluding inorganic compounds, colorants, and solvents) is appropriately selected depending on the purpose of use and is not particularly limited. However, in order to provide an obtained polymerizable composition with excellent curability, the total content of the optional components is preferably 50 parts by mass or less per 100 parts by mass of the polymerizable compound (B).

[0078] The polymerizable composition of the present invention can be irradiated with energy rays to form a cured product. The cured product is formed into an appropriate shape according to the application. For example, when forming a film-like cured product, the polymerizable composition of the present invention can be applied to a support substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, or plastic by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing methods, or immersion. In addition, after being applied once to a support substrate such as a film, it can also be transferred to another support substrate, and there is no limitation on the application method.

[0079] The light source of the energy rays used when curing the polymerizable composition of the present invention can be electromagnetic wave energy having a wavelength of 2000 angstroms to 7000 angstroms obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., and high energy rays such as electron beams, X-rays, and radiation. From the viewpoint of excellent curability of the resulting polymerizable composition, it is preferable to use ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light with a wavelength of 300 to 450 nm.

[0080] Furthermore, a laser direct writing method in which an image is formed directly from digital information from a computer or the like without using a mask by using a laser beam as an exposure light source is useful because it can improve not only productivity but also resolution and positional accuracy, and light with a wavelength of 340 to 430 nm is preferably used as the laser beam, but lasers emitting light in the visible to infrared range, such as excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, and YAG lasers, can also be used. When using these laser beams, a sensitizing dye that absorbs light in the visible to infrared range is preferably added because the resulting polymerizable composition has excellent curability.

[0081] Furthermore, in order to cure the polymerizable composition of the present invention, it is usually necessary to heat the composition after irradiation with the above energy rays, and heating to about 40 to 150° C. is preferred in terms of the cure rate.

[0082] The polymerizable compositions of the present invention are useful in the manufacture of photocurable paints or varnishes; photocurable adhesives; coatings for metals; printed circuit boards; color filters in liquid crystal display elements for color displays such as color televisions, PC monitors, personal digital assistants, digital cameras, etc.; color filters in CCD image sensors; electrode materials for plasma display panels; powder coatings; printing inks; printing plates; adhesives; dental compositions; gel coats; photoresists for electronics; electroplating resists; etching resists; dry films; solder resists; resists for producing color filters for various display applications or for forming structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; and resists for encapsulating electrical and electronic components. The present invention can be used for a variety of applications, including, but not limited to, compositions for forming dielectric layers in the sequential lamination of printed circuit boards; solder resists; magnetic recording materials; micromechanical components; waveguides; optical switches; plating masks; etching masks; color test systems; glass fiber cable coatings; screen printing stencils; materials for producing three-dimensional objects by stereolithography; materials for holographic recording; image recording materials; fine electronic circuits; bleaching materials; bleaching materials for image recording materials; bleaching materials for image recording materials which use microcapsules; photoresist materials for printed wiring boards; photoresist materials for UV and visible laser direct imaging systems; photoresist materials or protective films used to form dielectric layers in the sequential lamination of printed circuit boards.

[0083] The polymerizable composition of the present invention can be used for the purpose of forming a spacer for a liquid crystal display panel and for the purpose of forming a protrusion for a vertical alignment type liquid crystal display element, and is particularly useful as a photosensitive resin composition for simultaneously forming a protrusion and a spacer for a vertical alignment type liquid crystal display element.

[0084] The above-mentioned spacer for liquid crystal display panels is preferably formed by the steps of (1) forming a coating film of the polymerizable composition of the present invention on a substrate, (2) irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape, (3) baking after exposure, (4) developing the coating film after exposure, and (5) heating the coating film after development.

[0085] The polymerizable composition of the present invention to which a coloring material has been added is preferably used as a resist constituting each pixel of RGB, etc. in a color filter, or as a resist for a black matrix forming a partition wall of each pixel. Furthermore, in the case of a resist for a black matrix to which an ink repellent agent has been added, it is preferably used for a partition wall for an inkjet type color filter having a profile angle of 50° or more. As the ink repellent agent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant are preferably used.

[0086] When used as a partition wall for an ink-jet color filter, the partition wall formed from the polymerizable composition of the present invention partitions a transferee, and an optical element is manufactured by a method in which droplets are applied to the partitioned recesses on the transferee by an ink-jet method to form image areas. In this case, it is preferable that the droplets contain a colorant and the image areas are colored, and in that case, the optical element manufactured by the above manufacturing method has at least a pixel group consisting of a plurality of colored areas on a substrate and a partition wall separating each colored area of ​​the pixel group.

[0087] The polymerizable composition of the present invention can also be used as a protective film or insulating film composition. In this case, it may contain an ultraviolet absorber, alkylated modified melamine and / or acrylic modified melamine, mono- or di-functional (meth)acrylate monomer containing an alcoholic hydroxyl group in the molecule, and / or silica sol.

[0088] The insulating film is used for an insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable supporting substrate, the laminate is developable with an alkaline aqueous solution, and the insulating resin layer preferably has a thickness of 10 to 100 μm.

[0089] The polymerizable composition of the present invention can be used as a photosensitive paste composition by incorporating an inorganic compound therein. The photosensitive paste composition can be used to form fired patterns such as partition wall patterns, dielectric patterns, electrode patterns, and black matrix patterns of plasma display panels. EXAMPLES

[0090] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples, etc. The fact that the compounds obtained below are "liquid" means that they are liquid at atmospheric pressure and 25°C.

[0091] [Example 1] Synthesis of Compound 1 Compound 1 was synthesized according to the scheme shown below.

[0092] [ka]

[0093] (Synthesis of oxime 1) In a 100 ml four-neck flask, 1.0 eq. of 2-(4-((4-(2-methylbenzoyl)phenyl)thiol)phenyl)acetonitrile and 1.0 eq. of sodium hydroxide were added and dissolved in ethanol (100% by weight of theoretical yield), and the mixture was stirred in an ice bath at 5°C. 1.0 eq. of isobutyl nitrite dissolved in ethanol (100% by weight of theoretical yield) was added dropwise thereto. The reaction solution was returned to room temperature, stirred for 2 hours, filtered, and the filtrate was concentrated. Ethyl acetate was added thereto, and the mixture was washed three times with ion-exchanged water, dried over magnesium sulfate, and concentrated again. The residue was purified by silica gel column chromatography (eluent: ethyl acetate and hexane = 1:5) to obtain the target product as a brown viscous liquid compound in a yield of 60%.

[0094] (Synthesis of Compound 1) In a 100 ml four-neck flask, 1.0 eq. of oxime 1, dichloromethane (500% by weight of the theoretical yield), and 2.0 eq. of triethylamine were added and stirred on an ice bath at 5°C. 1.1 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling to 5°C again on an ice bath, 1.1 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 3 hours, and the solvent was distilled off under reduced pressure. Ethyl acetate and a 5% by mass aqueous NaOH solution were added thereto, and oil and water were separated. The organic layer was further washed three times with ion-exchanged water and then concentrated. Ethanol was added to the residue to perform crystallization, and the target product was obtained as a pale yellow powdery compound in a yield of 79%. The TG-DTA (melting point) measurement of the obtained compound, and 1 H-NMR measurements were performed, and the results are shown in Tables 1 and 2, respectively.

[0095] [Example 2] Synthesis of compound 2 Compound 2 was synthesized according to the scheme shown below.

[0096] [ka]

[0097] (Synthesis of oxime body 2) 1.0 eq. of 2,2,2-trifluoro-1-(4-((4-(2-methylbenzoyl)phenyl)thio)phenyl)ethan-1-one was added to a 100 ml four-neck flask and dissolved in ethanol (600% by weight of the theoretical yield). 1.2 eq. of hydroxyammonium chloride and 3.0 eq. of pyridine were added to the solution. The reaction mixture was refluxed for 3 hours, and the solvent was distilled off under reduced pressure. Ion-exchanged water was added thereto, and extraction was performed with ethyl acetate. The organic layer was washed with 5% by mass hydrochloric acid and ion-exchanged water in this order, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent: ethyl acetate and hexane = 1:5) to obtain the target product as a brown viscous liquid compound in a yield of 76%.

[0098] (Synthesis of Compound 2) The same procedure as in Example 1 was followed up to the water washing step, except that oxime body 1 was replaced with oxime body 2. The residue after concentration was purified by silica gel column chromatography (eluent: ethyl acetate and hexane = 1:5) to obtain the target compound as a yellow viscous liquid compound in a yield of 76%. 1 H-NMR measurements were performed, and the results are shown in Table 2.

[0099] [Example 3] Synthesis of compound 3 Compound 3 was synthesized according to the scheme shown below.

[0100] [ka]

[0101] (Synthesis of compound 3) In a 100 ml four-neck flask, 1.0 eq. of oxime 3, dichloromethane (600% by weight of theoretical yield), and 2.8 eq. of triethylamine were added and stirred on an ice bath at 0°C. 2.1 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling to 0°C again on an ice bath, 2.1 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed twice with a 1% by weight aqueous NaOH solution and three times with ion-exchanged water. The organic layer was dried and concentrated with magnesium sulfate, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:3). Ethanol (1500% by weight of theoretical yield) was added thereto to perform crystallization, and the target compound was obtained as a pale yellow powdery compound in a yield of 63%. The TG-DTA (melting point) measurement of the obtained compound, and 1 H-NMR measurements were performed, and the results are shown in Tables 1 and 2, respectively.

[0102] [Example 4] Synthesis of compound 4 Compound 4 was synthesized according to the scheme shown below.

[0103] [ka]

[0104] (Synthesis of oxime 4) 1.0 eq. of 1-(4-((4-nitrophenyl)thio)phenyl)dodecan-1-one was added to a 100 ml four-neck flask and dissolved in dimethylformamide (300% by weight of theoretical yield). 3.2 eq. of hydroxyammonium chloride and 3.2 eq. of sodium hydroxide were added to the solution. The reaction mixture was heated and stirred at 65°C for 2 hours, ion-exchanged water was added, and the mixture was extracted with ethyl acetate. After washing three times with ion-exchanged water, the organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:10). As a result, the target product was obtained as a pale yellow solid compound in a yield of 61%.

[0105] (Synthesis of compound 4) In a 100 ml four-neck flask, 1.0 eq. of oxime 4, dichloromethane (600% by weight of theoretical yield), and 2.0 eq. of triethylamine were added and stirred on an ice bath at 0°C. 1.3 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling to 0°C again on an ice bath, 1.3 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed twice with a 1% by mass aqueous NaOH solution and three times with ion-exchanged water. The organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:5). As a result, the target product was obtained as a light brown liquid compound in a yield of 72%. The obtained compound 1 H-NMR measurements were performed, and the results are shown in Table 2.

[0106] [Example 5] Synthesis of compound 5 Compound 5 was synthesized according to the scheme shown below.

[0107] [ka]

[0108] (Synthesis of oxime 5) 1.0 eq. of 1-(4-((4-nitrophenyl)thio)phenyl)dodecan-1-one was added to a 100 ml four-neck flask and dissolved in THF (350% by weight of the theoretical yield). 1.0 eq. of 4M HCl-ethyl acetate and 1.2 eq. of isobutyl nitrite were added thereto and stirred at 35°C for 3 hours. Methyl isobutyl ketone was added to the reaction solution, which was washed six times with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:8). As a result, the target product was obtained as a light brown liquid compound in 86% yield.

[0109] (Synthesis of Compound 5) The same procedure as in Example 1 was followed up to the water washing step, except that oxime body 1 was replaced with oxime body 5. The mixture was concentrated to obtain the target compound as a brown liquid compound in a yield of 41%. 1 H-NMR measurements were performed, and the results are shown in Table 2.

[0110] [Example 6] Synthesis of compound 6 Compound 6 was synthesized according to the scheme shown below.

[0111] [ka]

[0112] (Synthesis of compound 6) The same procedure as in Example 1 was followed up to the water washing step, except that oxime body 1 was replaced with oxime body 5 and piperidine was replaced with n-dibutylamine. The mixture was concentrated, and the residue was purified by silica gel column chromatography (eluent: ethyl acetate:hexane=1:7). As a result, the target product was obtained as a pale yellow liquid compound in a yield of 28%. 1 H-NMR measurements were performed, and the results are shown in Table 2.

[0113] [Example 7] Synthesis of compound 7 Compound 7 was synthesized according to the scheme shown below.

[0114] [ka]

[0115] (Synthesis of oxime 6) 1.0 eq. of 1-(4-((4-(thiophene-2-carbonyl)phenyl)thio)phenyl)ethan-1-one was added to a 100 ml four-neck flask and dissolved in dimethylformamide (400% by weight of the theoretical yield). 1.1 eq. of hydroxyammonium chloride and 1.1 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 55°C for 2 hours. Ethyl acetate (400% by weight of the theoretical yield) was added to the reaction solution, and ion-exchanged water (800% by weight of the theoretical yield) was added dropwise to carry out crystallization, obtaining the target product in a yield of 89%.

[0116] (Synthesis of compound 7) In a 100 ml four-neck flask, 1.0 eq. of oxime 6, dichloromethane (600% by weight of the theoretical yield), and 2.0 eq. of triethylamine were added and stirred on an ice bath at 0°C. 1.5 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling to 0°C again on an ice bath, 1.5 eq. of n-dibutylamine was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate was added thereto, and the mixture was washed twice with a 1% by mass aqueous NaOH solution and three times with ion-exchanged water. The organic layer was dried and concentrated with magnesium sulfate, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:15). As a result, the target product was obtained as a pale yellow solid compound in a yield of 59%. The TG-DTA (melting point) measurement of the obtained compound, and 1 H-NMR measurements were performed, and the results are shown in Tables 1 and 2, respectively.

[0117] [Example 8] Synthesis of compound 8 Compound 8 was synthesized according to the scheme shown below.

[0118] [ka]

[0119] (Synthesis of oxime 7) 1.0 eq. of 3-cyclohexyl-1-(4-((4-(2-methylbenzoyl)phenyl)thio)phenyl)propan-1-one was added to a 100 ml four-neck flask and dissolved in dimethylformamide (300% by weight of theoretical yield). 1.1 eq. of hydroxyammonium chloride and 1.1 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 60°C for 3 hours, ion-exchanged water was added, and the mixture was extracted with ethyl acetate. After washing three times with ion-exchanged water, the organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:8). As a result, the target product was obtained as a pale yellow solid compound in a yield of 60%.

[0120] (Synthesis of compound 8) The same procedure as in Example 1 was followed up to the water washing step, except that oxime body 1 was replaced with oxime body 7. The mixture was concentrated to obtain the target compound as a light brown liquid compound in a yield of 50%. 1 H-NMR measurements were performed, and the results are shown in Table 2.

[0121] [Comparative Example 1] Synthesis of Comparative Compound 1 Comparative compound 1 was synthesized according to the scheme shown below.

[0122] [ka]

[0123] (Synthesis of Comparative Compound 1) Except for changing n-dibutylamine to n-butylamine, the same procedure as in Example 7 was followed up to the water washing step. The mixture was concentrated, and the residue was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:8). As a result, the target substance was obtained as a pale yellow solid compound in a yield of 81%. The TG-DTA (melting point) measurement of the obtained compound and 1 H-NMR measurements were performed, and the results are shown in Tables 1 and 2, respectively.

[0124] [Table 1]

[0125] [Table 2]

[0126] [Examples 9 and 10 and Comparative Examples 2 and 3] Preparation of polymerizable compositions The blending shown in Table 3 was carried out to obtain polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2. The blending values ​​in the table indicate parts by mass. The symbols of each component in the table represent the following components. A-1: Compound 3 A-2: Compound 5 A'-3: Comparative compound 1 A'-4: Comparative compound 2 B-1: EPPN-201 (phenol novolac type epoxy resin, epoxy equivalent 193g / eq., manufactured by Nippon Kayaku Co., Ltd.) B-2: H-3M (phenolic resin, hydroxyl equivalent weight 105-109g / eq., manufactured by Meiwa Kasei Co., Ltd.) C-1: FZ-2122 (polyether modified polysiloxane, manufactured by Dow Corning Toray Co., Ltd., 1% by weight solution in PGMEA) D-1: Cyclopentanone (solvent)

[0127] [Table 3]

[0128] [ka]

[0129] [Evaluation Examples 1 and 2 and Comparative Evaluation Examples 1 and 2] The presence or absence of residual film was confirmed by the following procedure for the cured products of the polymerizable compositions 1 and 2 and the comparative polymerizable compositions 1 and 2. The results are shown in Table 5. Polymerizable compositions 1 and 2 and comparative polymerizable compositions 1 and 2 (coating amount: approximately 2 mL) were each coated onto a glass substrate (10 cm x 10 cm) using a spin coater (500 rpm x 2 seconds → 1000 rpm x 10 seconds → slope x 0.5 seconds), and the coated films were prebaked in an oven (90°C x 90 seconds) to form films. Each film was masked with a step tablet (33-step type, OD value 0-3, Table 4) with a gradation of continuously changing transmittance, and irradiated with a predetermined amount of ultraviolet light (illuminance 20 mW / cm) using a UV-LED (365 nm). 2 , exposure time 150 seconds, cumulative exposure 3000mJ / cm 2 ). After exposure, the film was post-baked in an oven (100° C.×20 min), developed (PGMEA, 30 sec) and rinsed (isopropyl alcohol, 10 sec). The number of remaining steps of the obtained cured film sample was visually confirmed. The number of remaining steps means the maximum number of steps in which the cured film remains. The transmittance was determined from the number of remaining steps according to Table 4, and the converted sensitivity was calculated using the following formula. Converted sensitivity (mJ / cm 2 ) = Accumulative exposure (3000mJ / cm 2 ) x transmittance (%) Table 5 shows the remaining number of plates and converted sensitivity.

[0130] [Table 4]

[0131] [Table 5]

[0132] From the results of Table 5 above, the polymerizable composition containing the carbamoyloxime compound of the present invention has a larger number of remaining steps (higher curability) than the comparative polymerizable composition, and therefore has a high photobase generation efficiency, can be cured with a low exposure dose, and is highly sensitive to a UV-LED light source. Therefore, it is clear that the compound of the present invention is excellent as a polymerization initiator.

[0133] [Example 11] Synthesis of compound 9 Compound 9 was synthesized according to the scheme shown below. [ka]

[0134] (Synthesis of oxime 8) 1.0 eq. of 1,1'-(thiobis(4,1-phenylene))bis(hexan-1-one) was added to a 100 ml four-neck flask and dissolved in dimethylformamide (400% by weight of the theoretical yield). 2.6 eq. of hydroxyammonium chloride and 2.6 eq. of pyridine were added to the solution. The reaction mixture was heated and stirred at 55°C for 7 hours, after which ion-exchanged water was added and extracted with ethyl acetate. The organic layer was washed three times with ion-exchanged water, dried over magnesium sulfate, and concentrated. 1,2-dichloroethane (12,000% by weight of the theoretical yield) was added to this and recrystallized to obtain the target product as a white powder in a yield of 77%.

[0135] (Synthesis of Compound 9) In a 100 ml four-neck flask, 1.0 eq. of oxime 8, dichloroethane (600% by weight of theoretical yield), and 4.0 eq. of triethylamine were added and stirred on an ice bath at 5°C. 3.0 eq. of 4-nitrophenyl chloroformate dissolved in dichloroethane (300% by weight of theoretical yield) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling to 5°C again on an ice bath, 3.0 eq. of aniline was added dropwise. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure. Ethyl acetate and ion-exchanged water were added thereto, and oil-water separation was performed. The organic layer was further washed three times with 1% by weight aqueous sodium hydroxide solution and twice with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate:toluene = 1:25) to obtain the target compound as a white powdery compound in a yield of 57%. The TG-DTA (melting point) measurement of the obtained compound, and 1 H-NMR measurements were performed, and the results are shown in Tables 6 and 7, respectively.

[0136] [Example 12] Synthesis of compound 10 Compound 10 was synthesized according to the scheme shown below.

[0137] [ka]

[0138] (Synthesis of compound 10) The same procedure as in Example 11 was followed up to the water washing step, except that aniline was replaced with 4-methylpiperidine. The residue after concentration was purified by silica gel column chromatography (eluent: ethyl acetate: toluene = 1:5) to obtain the target compound as a pale yellow viscous liquid compound in a yield of 80%. 1 H-NMR measurement was performed, and the results are shown in Table 7.

[0139] [Example 13] Synthesis of compound 11 Compound 11 was synthesized according to the scheme shown below.

[0140] [ka]

[0141] (Synthesis of oxime 9) 1.0 eq. of 1,1'-(thiobis(4,1-phenylene))bis(hexan-1-one) was added to a 100 ml four-neck flask and dissolved in dimethylformamide (350% by weight of theoretical yield). 2.0 eq. of 4M HCl-ethyl acetate and 2.5 eq. of isobutyl nitrite were added thereto and stirred at 45°C for 3 hours. Ethyl acetate was added to the reaction solution, which was washed four times with ion-exchanged water, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent = ethyl acetate:hexane = 1:5) to obtain the target product as a pale yellow solid in 72% yield.

[0142] (Synthesis of Compound 11) The same procedure as in Example 11 was followed up to the water washing step, except that oxime 1 was replaced with oxime 9 and aniline with dibutylamine. The residue after concentration was purified by silica gel column chromatography (eluent: ethyl acetate:toluene=1:20) to obtain the target compound as a pale yellow viscous liquid compound in a yield of 5%. 1 H-NMR measurement was performed, and the results are shown in Table 7.

[0143] [Table 6]

[0144] [Table 7] [Industrial Applicability]

[0145] The carbamoyloxime compound of the present invention has high photobase generation efficiency, and when used as a polymerization initiator, it can generate a base more efficiently than conventional photobase generators, and therefore can cure a polymerizable compound even at a low exposure dose. In particular, when used in a curable resin composition containing an epoxy resin or a phenol resin, it shows high curability.

Claims

1. A carbamoyl oxime compound represented by the following general formula (I): 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and R １０ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR １１ , -COOR １１ , -CO-R １１ , -SR １１ a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II): R ８ represents a group represented by the following general formula (II): R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ９ and R １０ at least one of which is a nitro group; R １１ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and R １１ When multiple are present, they may be the same or different, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ represents that one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR １２ , -COOR １２ , -CO-R １２ Or -SR １２ may be a group having 1 to 20 carbon atoms substituted with R １２ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and R １２ When multiple are present, they may be the same or different, <Group A> is -O-, -CO-, -COO-, -NR １３ --, --NR １３ CO- and -S-, R １３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １３ When multiple are present, they may be the same or different, R １ and R ２ , R ２ and R ３ , R ３ and R ４ , R ４ and R ５ , R ６ and R ７ , R ９ and R １０ may each independently be linked to each other to form a ring containing hydrogen atoms and carbon atoms and having 3 to 10 carbon atoms, When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups. 【Chemistry 2】 (In the formula, R ２０ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, X １ is -NR ２１ R ２２ or a group represented by the following general formula (a) or the following general formula (b): R ２１ and R ２２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, R ２０ , R ２１ and R ２２ represents that one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ２３ , -COOR ２３ , -CO-R ２３ Or -SR ２３ may be a group having 1 to 20 carbon atoms substituted with R ２３ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and ２３ When multiple are present, they may be the same or different, <Group B> is -O-, -CO-, -COO-, -NR ２４ --, --NR ２４ CO- and -S-, R ２４ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ２４ When multiple are present, they may be the same or different, R ２１ and R ２２ may be linked together to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, n represents 0 or 1; * represents a bond.) 【Chemistry 3】 (In the formula, R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ and R ４０ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>, R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ and R ４０ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ４１ , -COOR ４１ , -CO-R ４１ Or -SR ４１ may be a group having 1 to 20 carbon atoms substituted with R ４１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ４１ When multiple are present, they may be the same or different, <Group C> is -O-, -CO-, -COO-, -NR ４２ --, --NR ４２ CO- and -S-, R ４２ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ４２ When multiple are present, they may be the same or different, R ３１ and R ３２ , R ３３ and R ３４ , R ３５ and R ３６ , R ３７ and R ３８ , and R ３９ and R ４０ may each independently link to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, * represents a bond.)

2. A carbamoyl oxime compound represented by the following general formula (I): 【Chemistry 4】 (In the formula, R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ９ and R １０ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR １１ , -COOR １１ , -CO-R １１ , -SR １１ a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II): R １１ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and R １１ When multiple are present, they may be the same or different, R ３ and R ８ represents a group represented by the following general formula (II): R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ９ , R １０ and R １１ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR １２ , -COOR １２ , -CO-R １２ Or -SR １２ may be a group having 1 to 20 carbon atoms substituted with R １２ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and R １２ When multiple are present, they may be the same or different, <Group A> is -O-, -CO-, -COO-, -NR １３ --, --NR １３ CO- and -S-, R １３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １３ When multiple are present, they may be the same or different, R １ and R ２ , R ４ and R ５ , R ６ and R ７ , R ９ and R １０ may each independently be linked to each other to form a ring containing hydrogen atoms and carbon atoms and having 3 to 10 carbon atoms, When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups. 【Chemistry 5】 (In the formula, R ２０ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, X １ is -NR ２１ R ２２ or a group represented by the following general formula (a) or the following general formula (b): R ２１ and R ２２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, R ２０ , R ２１ and R ２２ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ２３ , -COOR ２３ , -CO-R ２３ Or -SR ２３ may be a group having 1 to 20 carbon atoms substituted with R ２３ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and ２３ When multiple are present, they may be the same or different, <Group B> is -O-, -CO-, -COO-, -NR ２４ --, --NR ２４ CO- and -S-, R ２４ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ２４ When multiple are present, they may be the same or different, R ２１ and R ２２ may be linked together to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, n represents 0 or 1; * represents a bond.) 【Chemistry 6】 (In the formula, R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ and R ４０ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>, R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ and R ４０ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ４１ , -COOR ４１ , -CO-R ４１ Or -SR ４１ may be a group having 1 to 20 carbon atoms substituted with R ４１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ４１ When multiple are present, they may be the same or different, <Group C> is -O-, -CO-, -COO-, -NR ４２ --, --NR ４２ CO- and -S-, R ４２ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ４２ When multiple are present, they may be the same or different, R ３１ and R ３２ , R ３３ and R ３４ , R ３５ and R ３６ , R ３７ and R ３８ , and R ３９ and R ４０ may each independently link to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, * represents a bond.)

3. A carbamoyl oxime compound represented by the following general formula (I): 【Chemistry 7】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and R １０ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR １１ , -COOR １１ , -CO-R １１ , -SR １１ a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II): R １１ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and R １１ When multiple are present, they may be the same or different, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR １２ , -COOR １２ , -CO-R １２ Or -SR １２ may be a group having 1 to 20 carbon atoms substituted with R １２ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and R １２ When multiple are present, they may be the same or different, <Group A> is -O-, -CO-, -COO-, -NR １３ --, --NR １３ CO- and -S-, R １３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １３ When multiple are present, they may be the same or different, R １ and R ２ , R ２ and R ３ , R ３ and R ４ , R ４ and R ５ , R ６ and R ７ , R ７ and R ８ , R ８ and R ９ , R ９ and R １０ may each independently be linked to each other to form a ring containing hydrogen atoms and carbon atoms and having 3 to 10 carbon atoms, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and R １０ At least one of the groups represented by the following general formula (II) is When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups. 【Chemistry 8】 (In the formula, R ２０ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, <Group B> is -O-, -CO-, -COO-, -NR ２４ --, --NR ２４ CO- and -S-, R ２４ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ２４ When multiple are present, they may be the same or different, X 1 represents a group represented by -NR 21 R 22 ; R ２１ and R ２２ are linked together to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, n represents 0 or 1; * represents a bond.)

4. A carbamoyl oxime compound represented by the following general formula (I): 【Chemistry 9】 (In the formula, R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ９ and R １０ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -OR １１ , -COOR １１ , -CO-R １１ , -SR １１ a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group represented by the following general formula (II): R ３ is -OR １１ , -COOR １１ , -CO-R １１ Or -SR １１ represents a group represented by R ８ represents a group represented by the following general formula (II): R １１ represents a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group A>, and R １１ When multiple are present, they may be the same or different, R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ９ , R １０ and R １１ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR １２ , -COOR １２ , -CO-R １２ Or -SR １２ may be a group having 1 to 20 carbon atoms substituted with R １２ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and R １２ When multiple are present, they may be the same or different, <Group A> is -O-, -CO-, -COO-, -NR １３ --, --NR １３ CO- and -S-, R １３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １３ When multiple are present, they may be the same or different, R １ and R ２ , R ４ and R ５ , R ６ and R ７ , R ９ and R １０ may each independently be linked to each other to form a ring containing hydrogen atoms and carbon atoms and having 3 to 10 carbon atoms, When a plurality of groups represented by general formula (II) are present in a molecule, they may be the same or different groups. 【Chemistry 10】 (In the formula, R ２０ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, X １ is -NR ２１ R ２２ or a group represented by the following general formula (a) or the following general formula (b): R ２１ and R ２２ each independently represents a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group B>, R ２０ , R ２１ and R ２２ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ２３ , -COOR ２３ , -CO-R ２３ Or -SR ２３ may be a group having 1 to 20 carbon atoms substituted with R ２３ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 1 to 20 carbon atoms in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group B>, or a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and ２３ When multiple are present, they may be the same or different, <Group B> is -O-, -CO-, -COO-, -NR ２４ --, --NR ２４ CO- and -S-, R ２４ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ２４ When multiple are present, they may be the same or different, R ２１ and R ２２ may be linked together to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, n represents 0 or 1; * represents a bond.) 【Chemistry 11】 (In the formula, R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ and R ４０ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with a divalent group selected from the following <Group C>, R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ and R ４０ is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ４１ , -COOR ４１ , -CO-R ４１ Or -SR ４１ may be a group having 1 to 20 carbon atoms substituted with R ４１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ４１ When multiple are present, they may be the same or different, <Group C> is -O-, -CO-, -COO-, -NR ４２ --, --NR ４２ CO- and -S-, R ４２ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ４２ When multiple are present, they may be the same or different, R ３１ and R ３２ , R ３３ and R ３４ , R ３５ and R ３６ , R ３７ and R ３８ , and R ３９ and R ４０ may each independently link to each other to form a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, nitrogen atoms, and carbon atoms, or a ring having 2 to 10 carbon atoms and consisting of hydrogen atoms, oxygen atoms, nitrogen atoms, and carbon atoms, * represents a bond.)

5. R in general formula (I) ８ The carbamoyl oxime compound according to claim 3, wherein is a group represented by the above general formula (II).

6. R in general formula (I) １ , R ２ , R4, R ５ , R ６ , R ７ , R ９ and R １０ At least one of the groups is -CO-R １１ The carbamoyl oxime compound according to claim 2, wherein

7. A carbamoyl oxime compound according to claim 3, wherein one or more of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 in general formula (I) are -CO-R11.

8. R in general formula (I) １ , R ２ , R4, R ５ , R ６ , R ７ , R ９ and R １０ The carbamoyl oxime compound according to claim 2, wherein at least one of the following is a nitro group:

9. A carbamoyl oxime compound according to claim 3, wherein one or more of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 in general formula (I) is a nitro group.

10. R in general formula (I) ３ and R ８ The carbamoyl oxime compound according to claim 1 or 3, wherein is a group represented by the above general formula (II).

11. X in formula (II) １ But -NR ２１ R ２２ and R ２１ and R ２２ are linked to each other to form a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, a nitrogen atom, and a carbon atom, or a ring having 2 to 10 carbon atoms and consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom.

12. X in formula (II) １ But -NR ２１ R ２２ and R ２１ is a hydrogen atom, R ２２ is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or R ２１ and R ２２ The carbamoyl oxime compound according to claim 1 or 2, wherein each of the is an aliphatic hydrocarbon group having 1 to 20 carbon atoms.

13. A latent base generator comprising the carbamoyl oxime compound according to any one of claims 1 to 12.

14. A polymerization initiator comprising the carbamoyl oxime compound according to any one of claims 1 to 12.

15. A polymerizable composition comprising the carbamoyl oxime compound according to any one of claims 1 to 12 and a polymerizable compound.

16. The polymerizable composition according to claim 15, wherein the polymerizable compound is an epoxy resin or an ethylenically unsaturated compound, or a mixture containing an epoxy resin and a phenolic resin, a mixture containing an epoxy resin and a thiol compound, or a mixture containing an ethylenically unsaturated compound and a thiol compound.

17. A cured product of the polymerizable composition according to claim 15 or 16.

18. A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to claim 15 or 16 with energy rays.

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