Compound, initiator, composition, cured product, and method for producing the cured product

Abstract

The present invention provides a compound represented by general formula (1). (In the formula, Ar is an aromatic ring group having two or more ring structures, A is a group having a quinuclidine skeleton, B- is a monovalent anion, and R1 and R2 are, for example, each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1-20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6-20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2-20 carbon atoms.)

Description

[Technical Field]

[0001] The present disclosure relates to a compound that can be used as an initiator, a composition containing the same, a cured product thereof, and a method for producing the cured product. [Background technology]

[0002] In general, photosensitive resin compositions are made by adding a photoinitiator to 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, etc.

[0003] Photoinitiators are classified into photoradical generators, photoacid generators, and photobase generators based on the active species generated upon irradiation with energy rays (light). Photoradical generators have advantages such as a fast curing rate and no residual active species after curing, but have the disadvantage that curing is inhibited by oxygen, necessitating the provision of an oxygen-blocking layer when curing thin films. Photoacid generators have the advantage of not being inhibited by oxygen, but have the disadvantage that residual acid from the active species can corrode metal substrates and denature the cured resin. Photobase generators have attracted attention because they are less likely to cause problems such as curing inhibition by oxygen and corrosion due to residual active species. Ionic photobase generators (Patent Document 1) and nonionic photobase generators (Patent Documents 2 and 3) are known. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO98 / 38195A1 [Patent Document 2] US20110233048A1 [Patent Document 3] International Publication No. 2010 / 064632 Summary of the Invention [Problem to be solved by the invention]

[0005] Ionic photobase generators tend to have better sensitivity than nonionic photobase generators, but have the drawback of insufficient storage stability. Furthermore, conventional photobase generators have the drawback of being unable to sufficiently promote curing of polymerizable compounds under low-temperature heating conditions due to their low polymerization catalytic ability.

[0006] The present disclosure has been made in consideration of the above problems, and aims to provide a compound that has excellent storage stability and polymerization catalytic activity, has good solubility in solvents, and can be used as an initiator. [Means for solving the problem]

[0007] The present inventors have conducted extensive research and found that by using a compound having an aromatic ring group with a specific structure and a group having a quinuclidine skeleton as a base generating group, the compound can be used as an initiator that has excellent storage stability and polymerization catalytic ability and good solvent solubility, and have thereby completed the present disclosure.

[0008] That is, the present disclosure provides a compound represented by the following general formula (1): [ka] (wherein Ar is an aromatic ring group having two or more ring structures, A is a group having a quinuclidine skeleton, B - is a monovalent anion, R 1 and R 2each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from the following Group I-1: The substituents substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, and the heterocycle-containing group having the above-mentioned substituent are atoms or groups selected from the following Group II-1: Group I-1: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-1: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

[0009] The compound represented by the above general formula (1) can be used as an initiator that has an excellent balance between storage stability and polymerization catalytic ability and good solvent solubility.

[0010] In the present disclosure, the aromatic ring group Ar having two or more ring structures is preferably an aromatic ring group represented by the following general formula (Ara1), (Arb1), or (Arc1), because the compound can be used as an initiator having an excellent balance between storage stability and polymerization catalytic activity. [ka] (In the formula, Y1 is a sulfur atom, CO, SO, SO2, CR 101 2. PR 102 or NR 102 and Y 2 is a single bond, oxygen atom, sulfur atom, CO, SO, SO2, CR 102 2. PR 102 or NR 101 and Y 3 are oxygen atoms, sulfur atoms, CO, SO, SO2, CR 102 2. PR 102 or NR 101 and R 101 each independently represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocycle-containing group are replaced with a divalent group selected from the following Group I-2: R 102 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from the following Group I-2: R 31 , R 32 , R 41 , R 42 , R 51 , R 52 and R 53 are each independently a halogen atom, a nitro group, a cyano group, -OR 121 , -COR 121 , -OCOR 121 , -COOR 121 , -SR 121 , -SOR 121, -SO2R 121 , -NR 122 R 123 , -NR 122 COR 123 , -CONR 122 R 123 an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group are replaced by a divalent group selected from the following Group I-2: However, multiple R 41 may be bonded to each other to form a ring, and the ring is unsubstituted or substituted; R 121 , R 122 and R 123 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group I-2; R 121 , R 122 or R 123 When there are a plurality of each of the groups, they may be the same or different, aliphatic hydrocarbon groups having the substituent, aromatic hydrocarbon ring-containing groups having the substituent, heterocyclic ring-containing groups having the substituent, and a plurality of R 41 a substituent substituting one or more hydrogen atoms in a ring formed by bonding these groups together is an atom or group selected from the following group II-2: a1 is an integer from 0 to 5, a2 is an integer from 0 to 4, b1 is an integer from 0 to 4, b2 is an integer from 0 to 3, c1 is an integer from 0 to 4, c2 is an integer between 0 and 1, * indicates the site of attachment. Group I-2: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-2: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

[0011] In the present disclosure, the group having a quinuclidine skeleton is a group represented by the following general formula (A1) or a group represented by formula (A2): 23 is particularly preferably a group in which R is an oxygen atom, and most preferably a group represented by formula (A1), because the compound can be used as an initiator having excellent solvent solubility due to the balance between storage stability and polymerization catalytic ability. [ka] (In the formula, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 111 , -COR 111 , -OCOR 111 , -COOR 111 , -SR 111 , -SOR 111 , -SO2R 111 , -NR 112 R 113 , -NR 112 COR 113, -CONR 112 R 113 an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the following group I-3, Or, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 two groups selected from the following are linked to each other to form a ring; X 11 and X 12 are each independently -CR 201 R 202 - is a divalent group represented by R 111 , R 112 and R 113 and R 201 and R 202 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group I-3; R 111 , R 112 , R 113 , R 201 and R 202 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, and the heterocycle-containing group having the above-mentioned substituent are atoms or groups selected from the following Group II-3: * indicates the site of attachment. Group I-3: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-3: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

[0012] In the present disclosure, the compound is preferably represented by the following general formula (11), because the compound has an excellent balance between storage stability and polymerization catalytic ability and can be used as an initiator with good solvent solubility. [ka] (In the formula, A + , B - , R 1 and R 2 is the same as in the above general formula (1), R 31 , R 32 a1 and a2 are the same as those in the general formula (Ara1) above.

[0013] In the present disclosure, among the compounds represented by general formula (1) or (11), R 1 is a hydrogen atom, R 2is preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from Group I-1. This is because the compound can be used as an initiator having an excellent balance between storage stability and polymerization catalytic ability.

[0014] In the present disclosure, among the compounds represented by general formula (1) or (11), the monovalent anion B - is preferably a borate anion, because the compound can be used as an initiator having an excellent balance between storage stability and polymerization catalytic ability.

[0015] The present disclosure provides an initiator comprising the above compound. According to the initiator of the present disclosure, since it contains the above compound, it has excellent storage stability and polymerization catalytic ability, and also has good solvent solubility.

[0016] The present disclosure provides a curable composition comprising the above compound and a curable component. The composition of the present disclosure contains the above-described compound, and therefore has excellent storage stability, curability, and solvent solubility.

[0017] The present disclosure provides a cured product of the above curable composition. According to the present disclosure, since the cured product is the curable composition described above, it is sufficiently cured and has excellent durability, for example.

[0018] The present disclosure provides a method for producing a cured product, the method comprising the step of curing the curable component in the curable composition. According to the present disclosure, the above-described curable composition is used, and therefore, a cured product that is sufficiently cured and has excellent durability and the like can be easily obtained. [Effects of the Invention]

[0019] The present disclosure provides a compound that can be used as an initiator having excellent storage stability and polymerization catalytic activity and good solvent solubility. The compound of the present disclosure also provides an initiator having excellent storage stability and polymerization catalytic activity and good solvent solubility, a composition having excellent storage stability and curability, and a cured product using the composition and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0020] The present disclosure relates to compounds, compositions, cured products thereof, and methods for producing the cured products. The compound, composition, cured product, and method for producing the cured product of the present disclosure will be described in detail below.

[0021] A. Compound 1. First, the compounds of the present disclosure will be described. One of the characteristics of the compound of the present disclosure is that it is represented by general formula (1).

[0022] [ka]

[0023] (wherein Ar is an aromatic ring group having two or more ring structures, A is a group having a quinuclidine skeleton, B - is a monovalent anion, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from the following Group I-1: The substituents substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, and the heterocycle-containing group having the above-mentioned substituent are atoms or groups selected from the following Group II-1: Group I-1: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-1: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

[0024] According to the present disclosure, a compound represented by general formula (1) (hereinafter sometimes referred to as Compound 1) has an aromatic ring group with a specific structure and a group having a quinuclidine skeleton as a base-generating group, and thus can be used as an initiator with an excellent balance of storage stability and polymerization catalytic activity and good solvent solubility. In this specification, "polymerization catalytic activity" refers not only to the polymerization catalytic activity of the base generated by the compound, but also to the "active species generating function" of the compound generating a base as an initiator. The polymerization catalytic activity of the base itself and the "active species generating function" of the compound provide a "progress-promoting function" for polymerization. Furthermore, the term "storage stability" refers to the suppression of the expression of the polymerization catalytic activity of the curable component before exposure. The storage stability can be confirmed, for example, by mixing the composition with the curable component to form a composition, and observing the degree of viscosity increase before and after a predetermined time has elapsed. The reason why the above-mentioned effect is achieved by having the above-mentioned predetermined structure is presumed to be as follows.

[0025] That is, the aromatic ring group having the specific structure has excellent light absorption properties in the region below visible light, and also facilitates the elimination of the group having the quinuclidine skeleton. Furthermore, the quinuclidine skeleton has a heterocyclic tertiary amine structure in which three alkyl chains bonded to the nitrogen atom each form a ring structure and one nitrogen atom is included as a ring skeleton-forming atom. By having such a structure, when the group having the quinuclidine skeleton is bonded to an aromatic ring group Ar, and is used in combination with a cyclic ether component such as an epoxy compound as a photosensitive resin composition, for example, the reaction with the cyclic ether component is suppressed, and the group exhibits excellent storage stability. Furthermore, when a group having a quinuclidine skeleton is eliminated from the aromatic ring group Ar, it becomes a base with little steric hindrance around the unshared electron pair on the nitrogen atom, thereby exhibiting excellent nucleophilicity. Furthermore, the quinuclidine skeleton structure provides excellent polymerization catalytic ability, for example, by efficiently exhibiting the catalytic action of a base. Furthermore, from the evaluation results in Table 11 below, it is believed that the skeletal structure of Compound 1 of the present invention contributes to improving solvent solubility.

[0026] For these reasons, the compound 1 can be used as an initiator that has an excellent balance between storage stability and polymerization catalytic activity and has good solvent solubility. Furthermore, when generating a base, Compound 1 also generates a radical, meaning that Compound 1 can be used not only as a base generator but also as a radical generator.

[0027] The compound of the present disclosure is represented by the above general formula (1). The compounds of the present disclosure will be described in detail below.

[0028] Above R 1 , R 2 and halogen atoms in Group II-1 (hereinafter referred to as "R 1 Examples of halogen atoms used in the above-mentioned processes include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0029] R in general formula (1) 1 , R 2An unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by the formula (hereinafter collectively referred to as "R 1 The aliphatic hydrocarbon group (used in the above-mentioned cases, etc.) may be any group that does not contain an aromatic hydrocarbon ring or a heterocyclic ring, and examples thereof include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, and groups in which one or more hydrogen atoms of these groups have been substituted with a substituent described below.

[0030] Above R 1 Examples of the alkyl group having 1 to 20 carbon atoms used in the above and the like include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl, tert-octyl, adamantyl, and the like.

[0031] Above R 1 Examples of the alkenyl group having 2 to 20 carbon atoms used in the above-mentioned formulas include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 4,8,12-tetradecatrienyl allyl, and cyclopentadienyl.

[0032] Above R 1The cycloalkyl group having 3 to 20 carbon atoms used in the above means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl.

[0033] Above R 1 The cycloalkylalkyl group having 4 to 20 carbon atoms used in the above means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl, and decahydronaphthylpropyl.

[0034] In the present disclosure, when a hydrogen atom in a group is substituted with a substituent, the number of carbon atoms in the group refers to the number of carbon atoms in the group after the substitution. For example, when a hydrogen atom in the alkyl group having 1 to 20 carbon atoms is substituted, the number of carbon atoms of 1 to 20 refers to the number of carbon atoms after the hydrogen atom is substituted, not the number of carbon atoms before the hydrogen atom is substituted. In the present disclosure, the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group is defined as the same as the number of carbon atoms in the group before the substitution. For example, in this specification, the number of carbon atoms in a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is replaced with a divalent group is defined as 1 to 20.

[0035] In addition, in the general formulas in the present disclosure, there may be multiple groups of the same symbol in one molecule (for example, R′), and in such cases, the present disclosure includes both cases where the multiple groups of the same symbol are the same and cases where they are different.

[0036] R in general formula (1) 1 , R 2 An unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, represented by the formula (hereinafter collectively referred to as "R 1 The "aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms" (also referred to as an "aromatic hydrocarbon ring-containing group represented by the formula (I) or (II)) may be any group that contains an aromatic hydrocarbon ring and does not contain a heterocycle, and examples thereof include an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a group having 6 to 20 carbon atoms in which an unsaturated aliphatic hydrocarbon group is substituted with an aryl group, and groups in which one or more hydrogen atoms of these groups are substituted with a substituent described below. In this specification, the "aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms" specifies the number of carbon atoms of the "aromatic hydrocarbon ring-containing group", not the "aromatic hydrocarbon ring". The same applies to cases with other numbers of carbon atoms.

[0037] Above R 1 The aryl group having 6 to 20 carbon atoms used in the above and the like is a group having aromaticity, and examples thereof include a group in which one hydrogen atom has been removed from a monocyclic aromatic ring such as phenyl (hereinafter, this may be referred to as a "monocyclic aromatic ring group"), a group in which one hydrogen atom has been removed from a fused ring of monocyclic aromatic rings such as naphthyl, anthracenyl, phenanthryl, pyrenyl, and fluorenyl (hereinafter, this may be referred to as a "fused aromatic hydrocarbon group"), and a group in which one or more hydrogen atoms have been removed from a compound in which two or more monocyclic aromatic rings and their fused rings, such as biphenyl and benzophenone, are bonded via a linking group such as a single bond, a carbonyl group (-CO-), or a sulfide group (-S-) (hereinafter, this may be referred to as a "linked aromatic hydrocarbon group"), as well as groups in which the hydrogen atoms in these aromatic rings have been substituted with aliphatic hydrocarbon groups, such as a tolyl group. Examples of the aliphatic hydrocarbon group that replaces the hydrogen atoms in the aromatic ring of the aryl group include the above-mentioned R 1 Examples of the aliphatic hydrocarbon group include the same groups as those exemplified above.

[0038] Above R 1Examples of the arylalkyl group having 7 to 20 carbon atoms used in the above-mentioned cases include groups in which one or more hydrogen atoms in the alkyl group have been substituted with the above-mentioned aryl group, such as benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl, as well as groups in which hydrogen atoms in these rings have been substituted with aliphatic hydrocarbon groups. Examples of the alkyl group in the arylalkyl group and the aliphatic hydrocarbon group substituting the hydrogen atom of the arylalkyl group include the above-mentioned R 1 Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include the same groups as those exemplified above as the aliphatic hydrocarbon group having 1 to 20 carbon atoms, represented by the following formula: Examples of the group having 6 to 20 carbon atoms in which the unsaturated aliphatic hydrocarbon group is substituted with an aryl group include groups in which one or more hydrogen atoms of the alkenyl group are substituted with the aryl group.

[0039] R in general formula (1) 1 , R 2 A heterocyclic ring-containing group having 2 to 20 carbon atoms and having an unsubstituted or substituted group, represented by the formula (hereinafter collectively referred to as "R 1 Examples of the heterocycle-containing group (also referred to as "heterocycle-containing group represented by the formula (I) or (II)") include heterocycles such as a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group, a morpholylfuran group, a thiophene group, a methylthiophene group, a hexylthiophene group, a benzothiophene group, a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, an imidazoline group, a pyrazole group, a pyrazolidine group, a piperidine group, and a piperazine group; groups in which one or two or more hydrogen atoms of a heterocycle are substituted with an aliphatic hydrocarbon group; and groups in which one or two or more hydrogen atoms of an aliphatic hydrocarbon group are substituted with a heterocycle; as well as groups in which one or two or more hydrogen atoms of these groups are substituted with a substituent described below. In addition, condensed rings of a heterocycle and an aromatic hydrocarbon ring (hereinafter sometimes referred to as condensed heterocycles), such as an indole ring, a quinoline ring, a benzofuran ring, a carbazole ring, a xanthene ring, and a thioxanthone ring, are also included in the heterocycle. The aliphatic hydrocarbon group includes the above-mentioned R 1Examples of the aliphatic hydrocarbon group include those exemplified as the aliphatic hydrocarbon group represented by the following formula: In this specification, the number "2 to 20" in the "heterocyclic ring-containing group having 2 to 20 carbon atoms" specifies the number of carbon atoms of the "heterocyclic ring-containing group," not the "heterocyclic ring." The same applies to other numbers of carbon atoms.

[0040] In the group in which two or more methylene groups of the above-mentioned aliphatic hydrocarbon group, aromatic hydrocarbon ring-containing group, or heterocyclic ring-containing group are replaced with divalent groups selected from the above-mentioned Group I-1, the divalent groups may be the same or different, but the oxygen atoms, sulfur atoms, or oxygen atoms and sulfur atoms are not adjacent to each other.Furthermore, in the group in which two or more methylene groups of the above-mentioned aliphatic hydrocarbon group, aromatic hydrocarbon ring-containing group, or heterocyclic ring-containing group are replaced with divalent groups selected from the above-mentioned Group I-1, the divalent groups selected from Group I-1 may not be adjacent to each other.This also applies to the following Group I-2, Group I-3, and other groups of divalent groups.

[0041] Examples of substituents substituting hydrogen atoms in the aliphatic hydrocarbon group, aromatic hydrocarbon ring-containing group, and heterocyclic ring-containing group described in relation to general formula (1), as well as in groups in which one or more methylene groups in these groups have been replaced by divalent groups selected from Group I-1, include, as Group II-1, halogen atoms, cyano groups, nitro groups, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH, and -SO3H. The unsubstituted aliphatic hydrocarbon groups used in R' and R" in Group II-1 and Group II-2 include the above-mentioned R 1 Among the aliphatic hydrocarbon groups listed above, R 1 Specifically, the unsubstituted aliphatic hydrocarbon group used for R' and R" can be an unsubstituted aliphatic hydrocarbon group having 1 to 19 carbon atoms. The unsubstituted aliphatic hydrocarbon group used for R' and R" can be an unsubstituted aliphatic hydrocarbon group having 1 to 19 carbon atoms, such as R 1Among the aliphatic hydrocarbon groups listed above, those having 1 to 19 carbon atoms can be used.

[0042] R used in general formula (1) 1 and R 2 are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group have been replaced with a divalent group selected from Group I-1. This is because the compound has an even better balance between storage stability and polymerization catalyst ability. In particular, R used in general formula (1) 1 and R 2 are all hydrogen atoms, or R 1 is a hydrogen atom, and R 2 is more preferably a group other than a hydrogen atom, because the compound has an even better balance between storage stability and polymerization catalyst ability.

[0043] Among them, R 2is preferably a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group or the aromatic hydrocarbon ring-containing group have been replaced with a divalent group selected from Group I-1, and more preferably a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 10 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group or the aromatic hydrocarbon ring-containing group have been replaced with a divalent group selected from Group I-1, and among these, a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a carbon atom Preferably, the alkyl group is an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or a group in which one or more methylene groups in the alkyl group or the aryl group have been replaced with a divalent group selected from Group I-1, particularly preferably a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted benzene ring-containing group having 6 to 10 carbon atoms, or a group in which one or more methylene groups in the alkyl group or the benzene ring-containing group have been replaced with a divalent group selected from Group I-1, even more preferably a hydrogen atom, an unsubstituted or substituted methyl group or ethyl group, or an unsubstituted or substituted phenyl group, and most preferably a hydrogen atom, an unsubstituted methyl group or ethyl group, or an unsubstituted phenyl group. This is because the compound has a better balance between storage stability and polymerization catalytic ability.

[0044] The quinuclidine skeleton in the group having a quinuclidine skeleton used for A in general formula (1) is a heterocyclic tertiary amine structure containing one nitrogen atom as a heteroatom forming a ring skeleton, and three alkyl chains bonded to the nitrogen atom each forming a ring structure. The group having a quinuclidine skeleton represented by A has a quinuclidine ring or a condensed ring of a quinuclidine ring and another ring. The group having a quinuclidine skeleton represented by A is formed by the unshared electron pair on the nitrogen atom of the quinuclidine ring, and is -CR of general formula (1). 1 R 2 - is particularly preferred in terms of the balance between storage stability and polymerization catalytic ability of compound 1, and solvent solubility. In particular, in compound 1, the group having a quinuclidine skeleton represented by A is preferably a group represented by the following general formula (A1) or general formula (A2). This is because the above compound can be used as an initiator with an excellent balance between storage stability and polymerization catalytic ability and with even better solvent solubility.

[0045] [ka] (In the formula, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 (Hereinafter referred to as “R 11 ~R 19 ") each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 111 , -COR 111 , -OCOR 111 , -COOR 111 , -SR 111 , -SOR 111 , -SO2R 111 , -NR 112 R 113 , -NR 112 COR 113 , -CONR 112 R 113an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the following group I-3, Or, R 11 ~R 19 two groups selected from the following are linked to each other to form a ring; X 11 and X 12 are each independently -CR 201 R 202 - is a divalent group represented by R 111 , R 112 and R 113 and R 201 and R 202 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, aromatic hydrocarbon ring-containing group, or heterocyclic ring-containing group have been replaced with a divalent group selected from the following group I-3; R 111 , R 112 , R 113 , R 201 and R 202 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, and the heterocycle-containing group having the above-mentioned substituent are atoms or groups selected from the following Group II-3: * indicates the site of attachment. Group I-3: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-3: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

[0046] [ka] (In the formula, R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 (Hereinafter referred to as “R 21 ~R 27 ") each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 111 , -COR 111 , -OCOR 111 , -COOR 111 , -SR 111 , -SOR 111 , -SO2R 111 , -NR 112 R 113 , -NR 112 COR 113 , -CONR 112 R 113 an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the following group I-4, Or, R 21 ~R 27 two groups selected from the following are linked to each other to form a ring; X 21 and X 22 are each independently -CR 201 R 202 - is a divalent group represented by R 111 , R 112 and R 113 and R 201 and R 202 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group I-4; R 111 , R 112 , R 113 , R 201 and R 202 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, and the heterocycle-containing group having the above-mentioned substituent are atoms or groups selected from the following Group II-4: X 23 represents an oxygen atom, =CR'R" or =N-OR"; R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. * indicates the site of attachment. Group I-4: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-4: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

[0047] R in general formula (A1) or (A2) 11 ~R 19 , R 21 ~R 27 , R 111 , R 112 and R 113 and R 201 and R 202 Examples of the halogen atom, the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, the unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or the unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms used in 1 Halogen atoms, R 1 Aliphatic hydrocarbon groups, R 1 Aromatic hydrocarbon ring-containing groups, such as R 1 As the heterocycle-containing group used in the above, those mentioned above can be used. As for R′ or R″ used in groups I-3, I-4, II-3, and II-4 of general formula (A1) or (A2), the same groups as those used in groups I-1, II-1, etc. can be used.

[0048] R used in general formula (A1) 11 ~R 19Examples of the ring formed by linking two groups selected from the above include an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring. Examples of the aliphatic hydrocarbon ring include a saturated aliphatic hydrocarbon ring or an unsaturated aliphatic hydrocarbon ring. Examples of the saturated aliphatic hydrocarbon ring include a cyclohexane ring and a cyclopentane ring. Examples of the unsaturated aliphatic hydrocarbon ring include a cyclohexene ring and a cyclopentadiene ring. Examples of the aromatic hydrocarbon ring include a benzene ring. R used in general formula (A2) 21 ~R 27 The ring formed by combining two groups selected from the group consisting of R 11 ~R 19 Examples of the ring formed by combining two groups selected from the group consisting of the above include those listed above.

[0049] The group having a quinuclidine skeleton used for A is a group represented by formula (A1) or a group represented by formula (A2), 23 is particularly preferably a group in which R is an oxygen atom, and most preferably a group represented by formula (A1), because the compound has an excellent balance between storage stability and polymerization catalytic ability and can be used as an initiator with even better solvent solubility.

[0050] In general formula (A1), R 11 ~R 19 is a hydrogen atom or other group or atom, but examples of substituents that are easily available as raw materials for producing Compound 1 include halogen atoms, nitro groups, cyano groups, -OR 111 , -COR 111 , -OCOR 111 , -COOR 111 , -SR 111 , -SOR 111 , -SO2R 111 , -NR 112 R 113 , -NR 112 COR 113 , -CONR 112 R 113 , an unsubstituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted aryl group having 6 to 10 carbon atoms; R 111 , R112 and R 113 are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms. R 11 ~R 19 is preferably a hydrogen atom or a group having 6 or less carbon atoms in terms of ease of production of compound 1.

[0051] In the present disclosure, R in general formula (A1) 11 ~R 19 are preferably all hydrogen atoms, or one to three of which are, as preferred substituents other than hydrogen atoms, hydroxyl groups, cyano groups, -SH groups, or unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms; more preferably all hydrogen atoms, or one or two of which are hydroxyl groups, cyano groups, -SH groups, or unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms, and the remainder being hydrogen atoms; even more preferably all hydrogen atoms, or one or two of which are hydroxyl groups, cyano groups, or -SH groups, and the remainder being hydrogen atoms; and most preferably all hydrogen atoms, or one or two of which are hydroxyl groups, and the remainder being hydrogen atoms. This is because the above compound has an excellent balance between storage stability and polymerization catalytic ability, and can be used as an initiator with better solvent solubility. R in general formula (A1) 11 ~R 19 is a substituent other than a hydrogen atom, R 13 , R 14 , R 16 and R 17 In these cases, it is preferable that either of R is a group or atom other than the above-mentioned hydrogen atom, and it is particularly preferable that either of R is a preferred substituent other than the above-mentioned hydrogen atom. 11 ~R 19 The remainder is preferably a hydrogen atom, because the compound can be used as an initiator having an excellent balance between storage stability and polymerization catalytic ability and further improved solvent solubility.

[0052] In general formula (A1), X 11 , X 12 As for R 201 and R 202 is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 3 or less carbon atoms, and R 201 and R 202 is more preferably a hydrogen atom or an unsubstituted alkyl group having 3 or less carbon atoms, and R 201 and R 202 is particularly preferably a hydrogen atom or a methyl group, and R 201 and R 202 is most preferably a hydrogen atom, because the compound can be used as an initiator having an excellent balance between storage stability and polymerization catalytic ability and further improved solvent solubility.

[0053] In general formula (A2), R 21 ~R 27 is a hydrogen atom or other group or atom, but groups or atoms that are easily available as raw materials for producing Compound 1 include halogen atoms, nitro groups, cyano groups, -OR 111 , -COR 111 , -OCOR 111 , -COOR 111 , -SR 111 , -SOR 111 , -SO2R 111 , -NR 112 R 113 , -NR 112 COR 113 , -CONR 112 R 113 , an unsubstituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted aryl group having 6 to 10 carbon atoms; R 111 , R 112 and R 113 are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms. 21 ~R 27 is preferably a hydrogen atom or a group having 6 or less carbon atoms in terms of ease of production of compound 1. 21 ~R 27In terms of ease of production, it is preferable that four or more of each of the groups be hydrogen atoms, and all of the groups may be hydrogen atoms.

[0054] In general formula (A2), X 21 , X 22 As for R 201 and R 202 is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 3 or less carbon atoms, and R 201 and R 202 is more preferably a hydrogen atom or an unsubstituted alkyl group having 3 or less carbon atoms, and R 201 and R 202 is particularly preferably a hydrogen atom or a methyl group, and R 201 and R 202 is most preferably a hydrogen atom, because Compound 1 has even better storage stability and polymerization catalytic activity.

[0055] The aromatic ring group Ar used in the general formula (1) is a group having two or more ring structures and having aromaticity. The aromatic ring group Ar includes R 1 The condensed aromatic hydrocarbon groups, linked aromatic hydrocarbon groups, R 1 and the like. Condensed heterocyclic groups in which one hydrogen atom has been removed from the condensed heterocyclic rings mentioned above as heterocyclic ring-containing groups can be used. More specifically, the aromatic ring group Ar is preferably a group represented by the following general formula (Ara1), (Arb1), or (Arc1), because the compound can be used as an initiator having an excellent balance between storage stability and polymerization catalytic activity.

[0056] [ka]

[0057] (In the formula, Y 1 is a sulfur atom, CO, SO, SO2, CR 101 2. PR 102 or NR 102 and Y 2 is a single bond, oxygen atom, sulfur atom, CO, SO, SO2, CR 102 2. PR 102 or NR 101 and Y 3 are oxygen atoms, sulfur atoms, CO, SO, SO2, CR 102 2. PR 102 or NR 101 and R 101 each independently represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocycle-containing group are replaced with a divalent group selected from the following Group I-2: R 102 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from the following Group I-2: R 31 , R 32 , R 41 , R 42 , R 51 , R 52 and R 53 are each independently a halogen atom, a nitro group, a cyano group, -OR 121 , -COR 121 , -OCOR 121 , -COOR 121 , -SR 121 , -SOR 121 , -SO2R 121 , -NR 122 R 123 , -NR 122 COR 123, -CONR 122 R 123 an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group are replaced by a divalent group selected from the following Group I-2: However, multiple R 41 may be bonded to each other to form a ring, and the ring is unsubstituted or substituted; R 121 , R 122 and R 123 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group I-2; R 121 , R 122 or R 123 When there are a plurality of each of the groups, they may be the same or different, aliphatic hydrocarbon groups having the substituent, aromatic hydrocarbon ring-containing groups having the substituent, heterocyclic ring-containing groups having the substituent, and a plurality of R 41 a substituent substituting one or more hydrogen atoms in a ring formed by bonding these groups together is an atom or group selected from the following group II-2: a1 is an integer from 0 to 5, a2 is an integer from 0 to 4, b1 is an integer from 0 to 4, b2 is an integer from 0 to 3, c1 is an integer from 0 to 4, c2 is an integer between 0 and 1, * indicates the site of attachment. Group I-2: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-2: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

[0058] where R in (Ara1), (Arb1) or (Arc1) 101 , R 102 , R 31 , R 32 , R 41 , R 42 , R 51 , R 52 , R 53 , R 121 , R 122 and R 123 Examples of the halogen atom, the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, the unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, and the unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms used in 1 Halogen atoms, R 1 Aliphatic hydrocarbon groups, such as R 1 Aromatic hydrocarbon ring-containing groups, such as R 1 As the heterocycle-containing group used in the above, those mentioned above can be used. For R′ or R″ used in groups I-2 and II-2 of general formulae (Ara1), (Arb1) and (Arc1), the same groups as those used in groups I-1, II-1 and the like can be used. Multiple R 41Examples of the ring formed by bonding these to each other include a benzene ring fused to the benzene ring located on the left side in Arb1, and examples of the structure of formula Arb1 having a ring formed therein include structures represented by the following formula (Arb1α), (Arb1β), or (Arb1γ).

[0059] [ka] ((Arb1α)~(Arb1β), R 43 represents an atom or group selected from Group II-2 above, b3 represents a number of 0 to 4, and b1' represents a number of 0 to 2. Y 2 , Y 3 , R 42 , b2 is the same as formula (Arb1). R 41 ' is plural R 41 R ' does not bond to each other to form a ring. 41 is the same as

[0060] In the present disclosure, the aromatic ring group Ar is preferably a group represented by the above general formula (Ara1) or (Arb1), and most preferably a group represented by formula (Ara1), because this provides the above compound 1 with particularly excellent curability and an excellent balance between storage stability and polymerization catalytic activity.

[0061] R in general formula (Ara1) 31 and R 32 are each independently a nitro group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 3 to 10 carbon atoms, or a group in which one or more methylene groups in these groups have been replaced by a divalent group selected from group I-2 above, or -COR 121 and R 121 is preferably an unsubstituted or substituted aryl group having 6 to 10 carbon atoms or an unsubstituted or substituted heterocycle-containing group having 3 to 10 carbon atoms, because the compound can be used as an initiator having an excellent balance between storage stability and polymerization catalytic ability.

[0062] In general formula (Ara1), a1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably an integer of 0 to 1, and most preferably 0. This is because compound 1 has an excellent balance between storage stability and polymerization catalyst ability.

[0063] In general formula (Ara1), a2 is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0. This is because compound 1 has an excellent balance between storage stability and polymerization catalyst ability.

[0064] The position of the bonding site in the general formula (Ara1), i.e., -CO-CR 1 R 2 A + B - The position of the bond to Y may be any position in the aromatic ring where it can be bonded. 1 The para position with respect to Y is preferred. This is because Compound 1 has a better balance between storage stability and polymerization catalyst ability, and exhibits better solvent solubility. In addition, it is easy to synthesize. Therefore, Y 1 When is a sulfur atom, the compound 1 is preferably a compound represented by the following general formula (11).

[0065] In the present invention, in the general formula (Ara1), Y 1 is a sulfur atom, CO, SO, NR 102 is preferred, and a sulfur atom is particularly preferred. This is because Compound 1 has an excellent balance between storage stability and polymerization catalytic activity. For the above reasons, among Compounds 1, the compound represented by the following formula (11) is preferred.

[0066] [ka] (In the formula, A + , B - , R 1 and R 2 is the same as in the above general formula (1), R 31 , R 32 a1 and a2 are the same as those in the general formula (Ara1) above.

[0067] R in general formula (Arb1) 41 and R 42 are each independently a nitro group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 3 to 10 carbon atoms, or a group in which one or more methylene groups in such an aliphatic hydrocarbon group or heterocyclic ring-containing group have been replaced by a divalent group selected from Group I-2 above, or -COR 121 and R 121 is an unsubstituted or substituted aryl group having 6 to 10 carbon atoms or an unsubstituted or substituted heterocyclic group having 3 to 10 carbon atoms, or R 41 It is preferred that they are bonded to each other to form a group represented by any one of the above (Arb1α) to (Arb1γ), because this provides compound 1 with even better storage stability and polymerization catalyst ability.

[0068] R 41 When they are not bonded to each other to form a ring, b1 in general formula (Arb1) is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably an integer of 0 to 1. This is because compound 1 has even better storage stability and polymerization catalytic ability.

[0069] R 41 When they are bonded to each other to form a ring and are represented by any one of formulas (Arb1α) to (Arb1β), b1′ is preferably 0 and b3 is preferably an integer of 0 to 1. This is because Compound 1 has even better storage stability and polymerization catalyst ability.

[0070] In general formula (Arb1) and the like, b2 is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0. This is because compound 1 has even better storage stability and polymerization catalyst ability.

[0071] The bonding site of the general formula (Arb1), i.e., -CO-CR 1 R 2 A + B - The bonding position of Y may be any available bonding position in the aromatic ring. 3 It is preferably meta or para to the above because Compound 1 has better storage stability and polymerization catalyst ability and exhibits better solvent solubility.

[0072] In the general formula (Arb1), Y 2 is preferably a single bond, and Y 3 is CR 102 2 or NR 101 This is because Compound 1 has better storage stability and polymerization catalyst ability, and is also easy to synthesize.

[0073] R 101 is preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the aliphatic hydrocarbon group have been replaced with a divalent group selected from Group I-2 above, and is particularly preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0074] R 102 is preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the aliphatic hydrocarbon group have been replaced with a divalent group selected from Group I-2 above, and is particularly preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, because Compound 1 has even better storage stability and polymerization catalyst ability.

[0075] Among compounds 1 in which the aromatic ring group is represented by formula (Arb1), compounds represented by the following formula (12) are preferred.

[0076] [ka] (In the formula, Y 3' is CR 102 2 or NR 101 and A + , B - , R 1 and R 2 is the same as in the above general formula (1), R 41 , R 42 , b1 and b2 are the same as those in the general formula (Arb1) above.)

[0077] B in the above general formula (1) - Examples of the monovalent anion represented by the formula (I) include halide ions, inorganic halide anions, sulfonate anions, phosphorus-containing anions, imide ions, borate anions (sometimes called "borate anions"), carboxylate anions, dithiocarbamate anions, organic sulfonylmethide ions, as well as thiocyanate anions and dithiocarbamate anions.

[0078] Examples of halide ions include chloride anions, bromide anions, iodide anions, and fluoride anions.

[0079] Examples of inorganic halide anions include perchlorate anion, chlorate anion, thiocyanate anion, hexafluorophosphate anion, antimony hexafluoride anion, arsenic hexafluoride anion, and boron tetrafluoride anion.

[0080] Examples of sulfonate anions include methanesulfonate ion, fluorosulfonate ion, benzenesulfonate anion, toluenesulfonate anion, 1-naphthylsulfonate anion, 2-naphthylsulfonate anion, trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, undecafluoropentanesulfonate anion, tridecafluorohexanesulfonate anion, pentadecafluoroheptanesulfonate anion, heptadecafluorooctanesulfonate ion, perfluoroethanesulfonate anion, Examples include fluoro-4-ethylcyclohexanesulfonate ion, N-alkyl (or aryl)diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5-nitrobenzenesulfonate anion, sulfonate anions described in JP 2004-53799 A, camphorsulfonate anion, fluorobenzenesulfonate anion, difluorobenzenesulfonate anion, trifluorobenzenesulfonate anion, tetrafluorobenzenesulfonate anion, and pentafluorobenzenesulfonate anion.

[0081] Examples of phosphorus-containing anions include alkyl esters or aryl esters of phosphoric acid or phosphonic acid, and organic group-substituted phosphinate anions in which the hydrogen atom bonded to the phosphorus atom in phosphinic acid ((HO)PH(=O)) is substituted with an alkyl group (e.g., having 1 to 20 carbon atoms) or an aryl group (e.g., having 6 to 20 carbon atoms), or a group in which the methylene group of these groups is substituted with a divalent group selected from Group I-1 above, such as —CO—. Examples include phosphate ester anions such as octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonylphenyl phosphate anion; phosphonate ester anions such as 2,2′-methylenebis(4,6-di-t-butylphenyl)phosphonate anion; and organic group-substituted phosphinate anions such as phenyl(2,4,6-trimethylbenzoyl)phosphinate, dialkyl phosphinate, and diphenyl phosphinate.

[0082] Examples of imide ions include bis(trifluoromethanesulfone)imide ion, bis(pentafluoroethanesulfone)imide ion, phthalimide ion, o-sulfobenzimidazole, bis(heptafluoropropanesulfone)imide ion, bis(nonafluorobutanesulfone)imide ion, bis(undecafluoropentanesulfone)imide ion, bis(pentadecafluoroheptanesulfone)imide ion, bis(tridecafluorohexanesulfone)imide ion, bis(heptadecafluorooctanesulfonimide) ion, (trifluoromethanesulfone)(nonafluorobutanesulfone)imide ion, (methanesulfone)(trifluoromethanesulfone)imide ion, and cyclohexafluoropropane-1,3-bis(sulfonyl)imide anion.

[0083] Examples of borate anions include organic anions in which an alkyl group and / or an aryl group is bonded to one of the bonds of a boron atom. Specific examples of borate anions include tetrakis(pentafluorophenyl)borate anion, tetrakis(4-fluorophenyl)borate anion, tetraphenylborate anion, tetraarylborate anions such as the borate anion described in JP-A-2007-112854, and triarylalkylborane anions. Other examples include the borate anion described in JP-A-6-184170 and the borate anion described in JP-A-2002-526391.

[0084] Examples of the carboxylate anion include a benzoate anion, a trifluoroacetate anion, and a 2-oxo-2-phenylacetate anion.

[0085] Examples of the methide ion include organic sulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide and tris(methanesulfonyl)methide. Examples of dithiocarbamate anions include N,N-diethyldithiocarbamate anion.

[0086] Other examples include alkyl sulfonate ions, fluoro-substituted alkyl sulfonate ions, alkyl sulfonimides, and fluoro-substituted alkyl sulfonimides substituted with an acryloyloxy group or a methacryloyloxy group, or with an aliphatic cyclic alkyl group such as a norbornyl group or an adamantyl group. In addition, quencher anions having the function of de-exciting (quenching) active molecules in an excited state, and metallocene compound anions such as ferrocene and luteocene having an anionic group such as a carboxy group, a phosphonic acid group, or a sulfonic acid group on the cyclopentadienyl ring, can also be used as needed.

[0087] B - Among the monovalent anions represented by the formula (I), from the viewpoint of a balance of low-temperature adhesion, storage stability, and ease of raw material availability, borate anions, thiocyanate anions, phthalimide anions, halide anions, sulfobenzimidide anions, tetrafluoroboron anions, phosphorus hexafluoride anions, trifluoromethanesulfonate anions, and phosphorus-containing anions are more preferred, and among these, borate anions and phosphorus-containing anions are preferred, with borate anions being particularly preferred, and borate anions represented by the following general formula (I) being most preferred. 301 ~R 304 is preferably an anion in which the alkyl group is an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, because the compound has a better balance between storage stability and catalytic performance.

[0088] [ka] (R 301 , R 302 , R 303 and R 304 are each independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, and the substituents are atoms or groups selected from Group II-5 below. Group II-5: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's, they may be the same or different.

[0089] Here, R in general formula (I) 301 , R 302 , R 303 and R 304 Examples of the unsubstituted alkyl group having 1 to 20 carbon atoms and the unsubstituted aryl group having 6 to 20 carbon atoms used in the above formula include R 1 Alkyl groups, such as those used in 1 As the aryl group used in the above, those mentioned above can be used. As for R' used in group II-5 of general formula (I), the same groups as those used in group II-1 can be used.

[0090] The method for producing the compound represented by the above general formula (I) is not particularly limited, but for example, it can be produced by the following method according to the following reaction scheme 1. That is, by reacting a ketone body in which bromine is bonded to the α-position of the carbonyl group with quinuclidine or a derivative thereof, a Br salt, Compound 1, is obtained. In Reaction Scheme 1, A is represented by general formula (A1), and R 11 ~R 19 is a hydrogen atom, and X 11 and X 12 is -CH2-, other compounds 1 can also be prepared by changing the quinuclidine derivative used.

[0091] [ka] (In the formula, R 1 and R 2 , Ar is the same as in general formula (1).

[0092] Compound 1, other than the Br salt, is the target anion B -and cations such as alkali metal cations M + The cation M can be obtained by reacting it with a salt of M (reaction formula 2 below). + Examples of the cation include sodium cation.

[0093] [ka] (In the formula, R 1 and R 2 , Ar is the same as in general formula (1).

[0094] Compound 1 can be used as a base generator or a radical generator, since it generates a base and a radical upon irradiation with light such as ultraviolet light or heating. In particular, Compound 1 is useful as a photobase generator and a photoradical generator. The base generator and the radical generator can be used as, for example, an initiator such as a photoinitiator or a thermal initiator. Examples of the photoinitiator include a photobase generator that cures a base-curable component by a base generated by light irradiation, and a photoradical initiator that polymerizes a radical-polymerizable component by the action of a radical generated by light irradiation. Examples of the thermal initiator include a thermal base generator that polymerizes a base-curable component by the action of a base generated by heating, and a thermal radical initiator that polymerizes a radical-polymerizable component by the action of a radical generated by heating. The base generator can also be used as a pH adjuster. In the present disclosure, the compound 1 is preferably used as an initiator, more preferably as a photoinitiator, and particularly preferably as a photobase generator, because this allows the compound 1 of the present disclosure to more effectively exhibit the effects of excellent storage stability and polymerization catalytic ability. In the present disclosure, the initiator refers to a polymerization initiator.

[0095] B. Initiator Next, the initiator of the present disclosure will be described. The initiator of the present disclosure contains the above-mentioned compound 1. Since the initiator of the present disclosure contains the above-mentioned compound 1, it has excellent storage stability and polymerization catalyst ability. Each component of the initiator of the present disclosure will be described in detail below.

[0096] 1. Compound 1 The type of compound 1 used in the initiator of the present disclosure may be any type that can provide an initiator with excellent storage stability and polymerization catalytic ability, and the initiator may contain only one type or two or more types.

[0097] The content of the compound 1 may be any amount that provides the desired storage stability, polymerization catalytic ability, and solvent solubility, and is appropriately determined depending on the type of initiator, etc. The content of the compound 1 can be, for example, 100 parts by mass in 100 parts by mass of the solid content of the initiator, that is, the solid content of the initiator can be made up of only the compound 1. The content of the compound 1 is less than 100 parts by mass per 100 parts by mass of the solid content of the initiator, i.e., the initiator may be a composition containing the compound 1 and other components, and can be, for example, more than 20 parts by mass and not more than 99.99 parts by mass. When the content of the compound 1 is within the above range, the initiator becomes excellent in storage stability, polymerization catalytic ability, and solvent solubility. The solid content refers to the total amount of all components other than the solvent.

[0098] The compound 1 can be the same as that described in the above section "A. Compound," and therefore, the description here will be omitted.

[0099] 2. Other ingredients The initiator may contain other components in addition to the compound 1. Such other components may include, for example, a solvent. The solvent is capable of dissolving or dispersing each component in the initiator. Therefore, even if the solvent is liquid at room temperature (25°C) and atmospheric pressure, the compound 1 is not included in the solvent. Either water or an organic solvent can be used as the solvent. In the present disclosure, the solvent is preferably an organic solvent, as this makes it easier to dissolve or disperse the compound 1.

[0100] Examples of the organic solvent include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and the monomethyl ether or monophenyl ether of dipropylene glycol monoacetate; cyclic ethers such as dioxane; esters such as ethyl formate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; and lactones such as γ-caprolactone, δ-caprolactone, and γ-butyrolactone.

[0101] The content of the solvent in the initiator can be 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the initiator.

[0102] Examples of other components besides the solvent include those described below in "2. Curable component" and "4. Additive" under "C. Composition." Examples of the other components include known compounds used as initiators such as base generators and radical initiators. The content of the other components can be appropriately set depending on the application of the initiator, etc., but can be, for example, 50 parts by mass or less, and preferably 10 parts by mass or less, per 100 parts by mass of the initiator, because this makes it easy to increase the content of compound 1 in the initiator, resulting in an initiator with excellent storage stability and polymerization catalytic ability.

[0103] 3.Other The initiator may be produced by any method as long as it contains the compound 1 in a desired amount. When the initiator contains Compound 1 and other components, a method using a known mixing means can be used.

[0104] The initiator may be used, for example, as an additive to a composition containing a curable component.

[0105] C. Composition Next, the composition of the present disclosure will be described. The composition of the present disclosure contains Compound 1 and a curable component. The composition of the present disclosure contains the above-mentioned compound, and therefore has excellent storage stability and curability.

[0106] Each component of the composition of the present disclosure will now be described in detail. 1. Compound 1 The type of compound 1 may be any type that can provide an initiator having excellent storage stability and polymerization catalytic ability, and the composition may contain only one type or two or more types.

[0107] The content of the compound 1 may be any amount that provides the desired storage stability and polymerization catalytic ability, but is preferably 0.2 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass, per 100 parts by mass of the solid content of the composition. This is because the composition has a better balance of storage stability and curability. In addition, the effects of the excellent polymerization catalytic ability of the compound 1 and the excellent curability of the composition are more effectively exhibited.

[0108] The content of Compound 1 may be any amount that provides the desired storage stability and polymerization catalytic ability, but is preferably from 0.2 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, and particularly preferably from 1 to 10 parts by mass, per 100 parts by mass of the composition, because this provides the composition with a better balance between storage stability and curability.

[0109] The content of Compound 1 may be any amount that provides the desired storage stability and polymerization catalytic ability, but is preferably from 0.2 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, and particularly preferably from 1 to 10 parts by mass, relative to 100 parts by mass of the curable component, because this provides the composition with a better balance between storage stability and curability.

[0110] The compound 1 can be the same as that described in the above section "A. Compound," and therefore, the description here will be omitted.

[0111] 2.Curing component The curable component used in the present disclosure is a component contained in the composition other than the above-mentioned compound 1, and may be any component that can be cured by the above-mentioned compound 1. Examples of the curable component include a base-curable component and a radical-polymerizable component, and the curable component may contain both a base-curable component and a radical-polymerizable component. In the present disclosure, it is particularly preferred that the curable component contains a base-curable component, because this allows the excellent storage stability and polymerization catalyst ability of Compound 1 contained in the composition to be more effectively exhibited.

[0112] Examples of the base-curable component include those that can be polymerized by the base generated from the compound 1 above. Such base-curable components include anionically polymerizable components and components that cure by a reaction catalyzed by a base.

[0113] The anionically polymerizable component may include one or more anionically polymerizable compounds having an anionically polymerizable group. Here, the anionically polymerizable group refers to a functional group that can be polymerized by a base generated from a photobase generator by exposure to active energy rays such as ultraviolet rays, and examples thereof include cyclic ether groups such as epoxy groups, episulfide groups, lactone rings, and lactam rings. Examples of anionically polymerizable compounds include epoxy compounds, episulfide compounds, and cyclic monomers (δ-valerolactone, ε-caprolactam).

[0114] Components that harden by a reaction catalyzed by a base include a mixture containing an epoxy compound and a hydroxyl group-containing compound (a ring-opening addition reaction between an epoxy compound and a hydroxyl group-containing compound such as a phenol compound), a mixture containing an epoxy compound and a compound having a carboxylic acid group (hereinafter sometimes referred to as a "carboxylic acid compound") (a ring-opening addition reaction between an epoxy compound and a compound having a carboxylic acid group), a mixture containing an epoxy compound and a thiol compound (a ring-opening addition reaction between an epoxy compound and a thiol compound), a mixture containing a compound having an ethylenically unsaturated group such as a methacrylate group (hereinafter sometimes referred to as an ethylenically unsaturated compound) and a thiol compound (Michael addition reaction ...methacrylate group and amine compounds (Michael addition reaction), mixtures containing carboxylic acid compounds and hydroxyl group-containing compounds (polyesterification reaction), mixtures containing carboxylic acid compounds and amine compounds (polyamidation reaction), polyamide compounds such as polyamic acid (polyimidization reaction by cyclodehydration), mixtures containing isocyanate compounds and hydroxyl group-containing compounds (polyurethane reaction by isocyanate and hydroxyl group-containing compounds such as alcohol compounds), alkoxysilane compounds (hydrolysis and polycondensation), mixtures containing isocyanate compounds and thiol compounds (polythiourethanization reaction), and cyanate ester compounds (triazine cyclization reaction by trimerization).

[0115] The radically polymerizable component includes ethylenically unsaturated compounds such as acrylate groups, methacrylate groups, and vinyl groups.

[0116] Epoxy compounds can include compounds containing epoxy groups. In addition to epoxy groups, compounds having hydroxyl groups such as ethylenically unsaturated groups, thiol groups, carboxy groups, acid anhydride structures, and phenolic groups can also be considered epoxy compounds. Examples of such epoxy compounds include the acid-reactive organic substances described in International Publication Nos. 2019 / 117162 and 2017 / 130896, and those described in International Publication Nos. 2014 / 084269 and 2016 / 132413. Specific examples include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds; polyglycidyl ether compounds of polynuclear polyhydric phenol compounds; glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids; homopolymers or copolymers of glycidyl methacrylate; epoxy compounds having glycidylamino groups; epoxidized products of cyclic olefin compounds; epoxidized conjugated diene polymers such as epoxidized polybutadiene; and heterocyclic compounds such as triglycidyl isocyanurate. The epoxy compound may also be a compound having an epoxy group and a radical polymerizable group, such as a compound in which one epoxy group of a bisphenol A type epoxy compound is acrylated.

[0117] The phenol compound used as the hydroxyl group-containing compound has a phenolic hydroxyl group, and examples of the compounds that can be used include those described in International Publication No. 2019 / 117162. Representative examples include bisphenol A phenolic resins, bisphenol E phenolic resins, phenol novolac resins, bisphenol A novolac phenolic resins, and aralkyl novolac phenolic resins. Examples of compounds having an alcoholic hydroxyl group (hereinafter sometimes referred to as alcohol compounds) used as the hydroxyl group-containing compound include polyols (polyfunctional alcohols) such as polyether polyols, polyester polyols, and polycarbonate polyols.

[0118] The ethylenically unsaturated compound may be a compound having an ethylenically unsaturated group but not having an epoxy group. Examples of such ethylenically unsaturated groups include those described in International Publication No. 2016 / 136752, JP 2016-210849 A, JP 2016-176009 A, and JP 2019-182862 A, such as unsaturated aliphatic hydrocarbons; unsaturated basic acids such as (meth)acrylic acid; mono(meth)acrylates of polymers having carboxy groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; unsaturated polybasic acids; esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols; metal salts of unsaturated polybasic acids; acid anhydrides of unsaturated polybasic acids; Examples of the vinyl amine compound include amides of unsaturated monobasic acids and polyamines; unsaturated aldehydes; unsaturated nitriles; unsaturated aromatic compounds such as styrene; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine; vinyl alcohols such as allyl alcohol; vinyl ethers such as vinyl methyl ether; unsaturated imides such as maleimide; indenes; aliphatic conjugated dienes such as 1,3-butadiene; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as polystyrene; vinyl urethane compounds, hydroxyl group-containing vinyl monomers, and vinyl epoxy compounds of polyepoxy compounds.

[0119] The thiol compound may be a compound having a thiol group but not having an epoxy group or an ethylenically unsaturated group. Those described in JP-A-2019-156801, JP-A-2017-117651, JP-A-2017 / 098798, etc. may be used, and examples thereof include compounds having one or more thiol groups in one molecule. Specific 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, Examples include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol thiol, 1,1,3,3-tetrakis(mercaptomethylthio)propane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, and trimethylolpropane trismercaptopropionate.

[0120] Examples of the carboxylic acid compound include a compound having a carboxy group capable of reacting with an epoxy group to form a covalent bond, and a compound having a structure that can be converted into a carboxy group. As the carboxylic acid compound, a compound having a carboxy group may be mentioned a polyfunctional carboxylic acid or acid chloride, for example, a polyfunctional aromatic carboxylic acid such as phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, or the like, or an acid chloride thereof, as well as a polyfunctional aliphatic carboxylic acid such as tetrahydrophthalic acid, hexahydrophthalic acid, or the like, or an acid chloride thereof. Furthermore, as the carboxylic acid compound, a compound having a structure that can be converted into a carboxy group, for example, an acid anhydride can also be used. Examples of acid anhydrides that can be used include those described in RE 2017 / 169985 and RE 2017 / 077846. Examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, and chlorendic anhydride.

[0121] As the acid anhydride, commercially available products can also be preferably used. Commercially available aromatic acid anhydrides include, for example, Rikacid MTA-15, TMGE-S, and TMTA-C (all manufactured by New Japan Chemical Co., Ltd.), and examples of aliphatic acid anhydrides include Rikacid OSA, MH-T, HNA-100, DDSA, TH, and HH (all manufactured by New Japan Chemical Co., Ltd.).

[0122] Examples of the isocyanate compound include diisocyanates, such as polyfunctional isocyanates as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.

[0123] Examples of the cyanate ester compound that can be used include the cyanate esters described in JP 2018-028009 A. Commercially available products include "LECy," "LVT-50," and "PT-30" manufactured by Lonza Japan.

[0124] The content of the curable component is preferably 60 parts by mass or more and 99.5 parts by mass or less, and more preferably 85 parts by mass or more and 99 parts by mass or less, per 100 parts by mass of the solid content of the composition, because this provides the composition with a better balance between storage stability and curability.

[0125] The content of the curable component is preferably 40 parts by mass or more and 99 parts by mass or less, and more preferably 60 parts by mass or more and 95 parts by mass or less, per 100 parts by mass of the composition, because this provides the composition with a better balance between storage stability and curability.

[0126] When the curable component contains an epoxy compound, the content of the epoxy compound is preferably 200 parts by mass or more and 7,000 parts by mass or less, and more preferably 400 parts by mass or more and 6,000 parts by mass or less, relative to 100 parts by mass of Compound 1. This is because the composition has an excellent balance between storage stability and curability.

[0127] When the curable component contains an ethylenically unsaturated compound in addition to an epoxy compound, the content of the ethylenically unsaturated compound is preferably 2 to 300 parts by mass, and more preferably 5 to 200 parts by mass, per 100 parts by mass of the epoxy compound, because the composition has a better balance between storage stability and curability.

[0128] When the curable component contains a thiol compound in addition to an epoxy compound or an ethylenically unsaturated compound, the content of the thiol compound is preferably 5 parts by mass or more and 150 parts by mass or less, and more preferably 15 parts by mass or more and 90 parts by mass or less, relative to 100 parts by mass of the total of the epoxy compound and the ethylenically unsaturated compound, because the composition has an excellent balance between storage stability and curability.

[0129] In the above amounts, compounds having an epoxy group and an ethylenically unsaturated group are considered to be epoxy compounds and are not included in the ethylenically unsaturated compounds, compounds having an epoxy group and a thiol group are considered to be epoxy compounds and are not included in the thiol compounds, and compounds having a thiol group and an ethylenically unsaturated group are considered to be ethylenically unsaturated compounds and are not included in the thiol compounds. Furthermore, when Compound 1 has a thiol group or an ethylenically unsaturated group, it is not included in either the thiol compounds or the ethylenically unsaturated compounds, and is included only in the amount of Compound 1.

[0130] 3. Solvent The composition may include a solvent to disperse or dissolve Compound 1 and the curable component. Even if the compound 1 and the curable component are liquid at room temperature (25°C) and atmospheric pressure, they are not included in the solvent. Either water or an organic solvent can be used as the solvent. In the present disclosure, the solvent is preferably an organic solvent, as this facilitates dissolving or dispersing the compound 1 and the like. The solvent can be the same as that described in the section "B. Initiator" above, and therefore a description thereof will be omitted here.

[0131] The content of the solvent is preferably 50 parts by mass or less, and is preferably 1 part by mass or more and 30 parts by mass or less, in terms of ease of handling and coating properties of the composition, in 100 parts by mass of the composition.

[0132] 4. Additives The composition may contain additives as necessary as components other than Compound 1, the curable component, and the solvent. The additives that can be used include those described as additives in WO 2019 / 117162, and examples thereof include inorganic compounds, colorants, latent epoxy curing agents, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, ultraviolet absorbers, antioxidants, antistatic agents, halogen-based compounds, phosphate ester compounds, phosphate amide compounds, fluororesins, metal oxides, flame retardants, hydrocarbons, lubricants, nucleating agents, crystallization agents such as crystallization accelerators, silane coupling agents, rubber elasticity imparting agents such as flexible polymers, and acid diffusion controllers.

[0133] The total content of additives (excluding inorganic compounds and coloring materials) is appropriately selected depending on the intended use and is not particularly limited, but is preferably 50 parts by mass or less per 100 parts by mass of the curable component, because this tends to make the composition more excellent in storage stability and curability.

[0134] 5. Composition The composition can be produced by any known method as long as it is capable of mixing the components in the desired amounts. For example, there can be mentioned a method in which the compound 1 is dissolved or dispersed in a solvent, and then a curable component is added to the solvent.

[0135] The applications of the above compositions include, for example, optical filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, sealants for semiconductor devices, LED packages, liquid crystal injection ports, organic EL devices, optical elements, electrical insulation, electronic components, and separation membranes, molding materials, putties, glass fiber impregnation agents, fillers, passivation films for semiconductors and solar cells, interlayer insulating films used in thin film transistors (TFTs), liquid crystal displays, organic EL displays, printed circuit boards, and the like, surface protective films, printed circuit boards, and color tiles. TVs, PC monitors, mobile information terminals, color filters for CCD image sensors, electrode materials for plasma display panels, printing inks, dental compositions, resins for stereolithography, both liquid and dry films, micromechanical parts, glass fiber cable coatings, holographic recording materials, magnetic recording materials, optical switches, plating masks, etching masks, stencils for screen printing, touch panels such as transparent conductive films, MEMS elements, nanoimprint materials, photofabrication such as two-dimensional and three-dimensional high-density mounting of semiconductor packages, decorative sheets, artificial nails, glass It can be used for a variety of applications, including alternative optical films, electronic paper, optical discs, microlens arrays used in projectors and optical communication lasers, etc., prism lens sheets used in backlights of LCD displays, Fresnel lens sheets used in screens of projection televisions, etc., lens portions of lens sheets such as lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses and imaging lenses, optical elements, optical connectors, optical waveguides, insulating packing, heat-shrinkable rubber tubing, O-rings, sealants for display devices, protective materials, optical fiber protective materials, adhesives, die bonding agents, high heat dissipation materials, high heat-resistant sealants, solar cell, fuel cell, and secondary battery components, solid electrolytes for batteries, insulating coating materials, photosensitive drums for copiers, gas separation membranes, civil engineering and construction materials such as concrete protective materials, linings, soil injection agents, sealants, heat storage materials, glass coatings, and foams, tubes, sealants, coating materials, sealants for sterilization treatment equipment, contact lenses, oxygen-enriched membranes, medical materials such as biochips, automotive parts, and various machine parts.

[0136] D. Cured product Next, the cured product of the present disclosure will be described. The cured product of the present disclosure is a cured product of the composition of the present disclosure. According to the present disclosure, since it is a cured product of the above-mentioned curable composition, it is sufficiently cured and has excellent durability, for example.

[0137] The cured product of the present disclosure uses the above-described composition. The contents of the composition can be the same as those described in the section "C. Composition" above, and therefore a description thereof will be omitted here. The cured product may be any product containing a high molecular weight product formed by a polymerization reaction of the curable component. The shape of the cured product in plan view can be appropriately set depending on the application of the cured product, and may be, for example, a pattern such as a dot shape or a line shape.

[0138] The uses of the cured product may be the same as those described in the section "C. Composition" above.

[0139] The method for producing the cured product is not particularly limited as long as it is a method that can form the cured product of the composition into a desired shape. As such a production method, for example, the production method described in the section "E. Production method of cured product" below can be used.

[0140] E. Manufacturing method of cured product Next, a method for producing the cured product of the present disclosure will be described. The method for producing a cured product according to the present disclosure includes a curing step of curing the above-described composition. Each step of the manufacturing method of the present disclosure will be described in detail below.

[0141] 1.Curing process The curing step is a step of curing the composition. The method for curing the composition may be any method that allows a curable component in the composition to undergo a polymerization reaction to obtain a high molecular weight product. Such a polymerization method can include a method that can generate a base and radicals from the above-mentioned compound 1, and specifically, a method can be used in which the above-mentioned composition is subjected to a light irradiation treatment to polymerize the curable components together.

[0142] In the case of light irradiation, the light irradiated to the composition may include light having a wavelength of 300 nm to 450 nm. Examples of energy ray sources used to cure the composition include high-energy rays such as electromagnetic wave energy having a wavelength of 2,000 angstroms to 7,000 angstroms, electron beams, X-rays, and radioactive rays, which are 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, and CRT light sources. Ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, and xenon arc lamps that emit light having a wavelength of 300 to 450 nm are preferred. Laser light may also be used as the irradiated light. Laser light having a wavelength of 340 to 430 nm may be used. As the light source of the laser light, those that emit light in the visible to infrared region, such as an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser, can also be used. Since Compound 1 has excellent photobase generating ability, the composition of the present disclosure may be cured by heating the coating film after irradiation with the energy rays. If heating is performed, heating at about 40 to 150°C is preferred in terms of the curing rate, but in the present disclosure, a low temperature such as 80°C or lower can be used. If heating is performed, the heating time is usually 1 to 120 minutes.

[0143] 2. Other processes The method for producing the cured product may include other steps in addition to the curing step, if necessary. Examples of the other steps include a developing step in which unpolymerized portions in the coating film of the composition are removed after the curing step to obtain a patterned cured product; a post-baking step in which the cured product is heat-treated after the curing step; a pre-baking step in which the composition is heat-treated to remove the solvent in the composition before the curing step; and a step in which a coating film of the composition is formed before the curing step.

[0144] As a method for removing the unpolymerized portions in the development step, for example, an alkaline developer can be applied to the unpolymerized portions. As the alkaline developer, those generally used as alkaline developers such as an aqueous solution of tetramethylammonium hydroxide (TMAH) or an aqueous solution of potassium hydroxide can be used. The developing step may be carried out at any time after the curing step. The heating conditions in the pre-baking step may be any conditions that can remove the solvent in the composition, and may be, for example, at 70° C. or higher and 150° C. or lower for 30 to 300 seconds. The heating conditions in the post-baking step may be any conditions that can improve the strength of the cured product obtained in the curing step, and may be, for example, 200° C. or higher and 250° C. or lower for 20 to 90 minutes. In the step of forming the coating film, the composition can be applied by any known method such as using a spin coater, roll coater, bar coater, die coater, curtain coater, various types of printing, or dipping. The coating film can be formed on a substrate. Furthermore, after the cured product is formed on a substrate, it may be peeled off from the substrate and used, or may be transferred from the substrate to another adherend and used.

[0145] 3.Other The cured product produced by the above production method and its uses can be the same as those described in the section "C. Composition" above.

[0146] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included within the technical scope of the present disclosure. [Example]

[0147] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited to these examples.

[0148] [Production Example 1] Synthesis of Br Salt Intermediate 1 1.0 eq. of 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one was added to a flask and dissolved in tetrahydrofuran (1,000% by weight of the theoretical yield). 1.1 eq. of quinuclidine was added thereto and stirred at room temperature for 2 hours. The reaction solution was concentrated to obtain the target product as a pale yellow powder compound in 100% yield.

[0149] [ka]

[0150] [Production Example 2] Synthesis of Br salt intermediate 2 The reaction was carried out in the same manner as in Production Example 1, except that quinuclidine in Production Example 1 was changed to 3-quinuclidinol. The precipitate was collected by suction filtration, and the target product was obtained as a white powder compound in a yield of 93%.

[0151] [ka]

[0152] [Production Example 3] Synthesis of Br salt intermediate 3 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one was used instead of 2-bromo-1-(4-(phenylthio)phenyl)ethan-1-one. The target product was obtained as a white powdery compound in a yield of 77%.

[0153] [ka]

[0154] [Production Example 4] Synthesis of Br salt intermediate 4 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one was used instead of 2-bromo-1-(4-(phenylthio)phenyl)butan-1-one and the reaction conditions were refluxed for 5 hours. The target product was obtained as a white powdery compound in a yield of 62%. [ka]

[0155] [Example 1] Synthesis of compound (1) 1.0 eq. of Br salt intermediate 1 was added to the flask and dissolved in chloroform (500% by weight of the theoretical yield). In a separate container, 1.1 eq. of sodium tetraphenylborate was dissolved in ion-exchanged water (500% by weight of the theoretical yield), and this solution was added to the flask. After stirring at room temperature for 1 hour, the reaction mixture was separated into oil and water, and the aqueous layer was discarded. After further washing with ion-exchanged water three times, the organic layer was concentrated, and the target product was obtained as a pale yellow powder compound in a yield of 95%. Regarding the compound obtained, 1 The results were analyzed using H-NMR and UV-Vis, and are shown in Tables 1 and 2.

[0156] [ka]

[0157] [Example 2] Synthesis of compound (2) The same procedure as in Example 1 was carried out, except that Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 2. The target product was obtained as a pale yellow powdery compound in a yield of 89%. 1 The results were analyzed using H-NMR and UV-Vis, and are shown in Tables 1 and 2.

[0158] [ka]

[0159] [Example 3] Synthesis of compound (3) The same procedure as in Example 1 was carried out, except that Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 3. The target product was obtained as a white powder compound in a yield of 84%. 1 The results were analyzed using H-NMR and UV-Vis, and are shown in Tables 1 and 2.

[0160] [ka]

[0161] [Example 4] Synthesis of compound (4) The same procedure as in Example 1 was carried out, except that Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 4. The target product was obtained as a white powder compound in a yield of 80%. 1 The results were analyzed using H-NMR and UV-Vis, and are shown in Tables 1 and 2.

[0162] [ka]

[0163] [Table 1]

[0164] [Table 2]

[0165] [Production Example 5] Synthesis of Br Salt Intermediate 5 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one was used instead of 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)propan-1-one and the reaction conditions were refluxed for 3 hours. The target product was obtained as a white powdery compound in a yield of 57%.

[0166] [ka]

[0167] [Production Example 6] Synthesis of Br salt intermediate 6 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one described in Production Example 2 was replaced with 2-bromo-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)butan-1-one and the reaction conditions were refluxed for 9 hours. The target product was obtained as a yellow powdery compound in a yield of 64%.

[0168] [ka]

[0169] [Production Example 7] Synthesis of Br Salt Intermediate 7 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one described in Production Example 2 was replaced with methyl 2-(6-(2-bromobutanoyl)-9-ethyl-9H-carbazol-3-yl)-2-oxoacetate and the reaction conditions were refluxed for 9 hours. The target product was obtained as a pale yellow powdery compound in a yield of 57%.

[0170] [ka]

[0171] [Production Example 8] Synthesis of Br salt intermediate 8 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one described in Production Example 2 was replaced with 2-bromo-1-(7-(2-methylbenzoyl)-9H-fluoren-2-yl)butan-1-one and the reaction conditions were refluxed for 8 hours. The target product was obtained as a yellow powdery compound in a yield of 80%.

[0172] [ka]

[0173] [Production Example 9] Synthesis of Br salt intermediate 9 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one described in Production Example 2 was replaced with methyl 2-(7-(2-bromobutanoyl)-9H-fluoren-2-yl)-2-oxoacetate and the reaction conditions were refluxed for 8 hours. The target product was obtained as a yellow powdery compound in a yield of 75%.

[0174] [ka]

[0175] [Production Example 10] Synthesis of Br Salt Intermediate 10 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one described in Production Example 2 was replaced with 2-bromo-1-(4-bromo-11-(2-ethylhexyl)-11H-benzo[a]carbazol-8-yl)butan-1-one and the reaction conditions were refluxed for 9 hours. The target product was obtained as a white powdery compound in a yield of 33%.

[0176] [ka]

[0177] [Production Example 11] Synthesis of Br Salt Intermediate 11 The reaction was carried out in the same manner as in Production Example 4, except that 3-quinuclidinone was used instead of 3-quinuclidinol. The precipitate was collected by suction filtration, and the target product was obtained as a white powder compound in a yield of 60%.

[0178] [ka]

[0179] [Production Example 12] Synthesis of Br salt intermediate 12 The reaction was carried out in the same manner as in Production Example 4, except that 3-quinuclidinol was replaced with 4-cyanoquinuclidine. The precipitate was collected by suction filtration, and the target product was obtained as a white powder compound in a yield of 65%.

[0180] [ka]

[0181] Comparative Preparation Example 1: Synthesis of Br Salt Intermediate 13 The same procedure as in Production Example 2 was repeated, except that 2-bromo-2-phenyl-1-(4-(phenylthio)phenyl)ethan-1-one was replaced with 4-(bromoethyl)-7-methoxy-2H-chromen-2-one. The target product was obtained as a pale yellow powder in a yield of 93%.

[0182] [ka]

[0183] [Comparative Example 1] Synthesis of Comparative Compound 2 The same procedure as in Example 1 was carried out, except that the Br salt intermediate 1 described in Example 1 was changed to the Br salt intermediate 13. The target product was obtained as a pale yellow powdery compound in a yield of 96%.

[0184] [ka]

[0185] Comparative Preparation Example 2: Synthesis of Br Salt Intermediate 14 The same procedure as in Production Example 3 was carried out, except that 1-methylpiperidine was used instead of 3-quinuclidinol. The target product was obtained as a white powder compound in a yield of 87%.

[0186] [ka]

[0187] [Comparative Example 2] Synthesis of Comparative Compound 3 The same procedure as in Example 1 was carried out, except that the Br salt intermediate 1 described in Example 1 was changed to the Br salt intermediate 14. The target product was obtained as a white powder compound in a yield of 98%.

[0188] [ka]

[0189] [Example 5] Synthesis of compound (5) The Br salt intermediate 2 used in Example 2 was directly used as compound (5). [ka]

[0190] [Example 6] Synthesis of compound (6) The same procedure as in Example 1 was carried out, except that Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 5. The target product was obtained as a white powder compound in a yield of 67%.

[0191] [ka]

[0192] [Example 7] Synthesis of compound (7) The same procedure as in Example 1 was carried out, except that the Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 6. The target product was obtained as a white powder compound in a yield of 78%.

[0193] [ka]

[0194] [Example 8] Synthesis of compound (8) The same procedure as in Example 1 was carried out, except that Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 7. The target product was obtained as a white powder compound in a yield of 70%.

[0195] [ka]

[0196] [Example 9] Synthesis of compound (9) The same procedure as in Example 1 was carried out, except that Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 8. The target product was obtained as a white powder compound in a yield of 68%.

[0197] [ka]

[0198] [Example 10] Synthesis of compound (10) The same procedure as in Example 1 was carried out, except that Br salt intermediate 1 described in Example 1 was changed to Br salt intermediate 9. The target product was obtained as a white powder compound in a yield of 72%.

[0199] [ka]

[0200] [Example 11] Synthesis of compound (11) The same procedure as in Example 1 was carried out, except that the Br salt intermediate 1 described in Example 1 was changed to the Br salt intermediate 10. The target product was obtained as a yellow solid compound in a yield of 86%.

[0201] [ka]

[0202] [Example 12] Synthesis of compound (12) The same procedure as in Example 3 was carried out, except that sodium tetraphenylborate described in Example 3 was changed to sodium phenyl(2,4,6-trimethylbenzoyl)phosphinate. The target product was obtained as a white powdery compound in a yield of 92%.

[0203] [ka]

[0204] [Example 13] Synthesis of compound (13) The same procedure as in Example 1 was carried out, except that the Br salt intermediate 1 described in Example 1 was changed to the Br salt intermediate 11. The target product was obtained as a white powder compound in a yield of 68%.

[0205] [ka]

[0206] [Example 14] Synthesis of compound (14) The same procedure as in Example 1 was carried out, except that the Br salt intermediate 1 described in Example 1 was changed to the Br salt intermediate 12. The target product was obtained as a white powder compound in a yield of 67%.

[0207] [ka]

[0208] [Example 15] Synthesis of compound (15) The same procedure as in Example 2 was carried out, except that sodium tetraphenylborate was changed to sodium thiocyanate. The target product was obtained as a white powdery compound in a yield of 80%.

[0209] [ka]

[0210] Regarding the obtained compounds (5) to (15) and comparative compounds 2 and 3, 1 The results are shown in Tables 3 to 5.

[0211] [Table 3]

[0212] [Table 4]

[0213] [Table 5]

[0214] [Rating 1] Compositions were prepared according to the formulations shown in the following Tables 6 to 10 (Examples 21 to 53 and Comparative Examples 3 to 7). The values ​​in the tables represent parts by mass. The symbols of the components in the table represent the following components: Some structures of the following components are shown below.

[0215] (Base-curable component 1: epoxy compound) A1: A compound represented by the following formula (A-1) (bisphenol A epoxy compound) A2: A compound represented by the following formula (A-2) (bisphenol E type epoxy compound) A3: A compound represented by the following formula (A-3) (EPPN201, Nippon Kayaku Co., Ltd.) A4: Compounds represented by the following formula (A-4) (aliphatic epoxy compounds, aliphatic ring-containing epoxy compounds, hydrogenated bisphenol A epoxy compounds) A5: A compound represented by the following formula (A-5) (Daicel Corporation, Celloxide 2021P) A6: A compound represented by the following formula (A-6) (ADEKA ED-506, epoxy equivalent 300 g / eq) A7: Acrylonitrile butadiene modified epoxy compound (ADEKA EPR-4030, epoxy equivalent 365g / eq) A8: 4-Hydroxybutyl acrylate glycidyl ether (4HBAGE) A9: A compound represented by the following formula (A-9) (a reaction product of a compound represented by the following formula (A-1) with acrylic acid)

[0216] [ka]

[0217] (Base-curing component 2: thiol compound) B1: A compound represented by the following formula (B-1) (PEMP, weight-average molecular weight 488.64, functional group 4, SC Organic Chemicals Co., Ltd.) B2: A compound represented by the following formula (B-2) (TEMPIC, weight-average molecular weight 525.6, functional group 3, SC Organic Chemicals) B3: A compound represented by the following formula (B-3) (TMMP, weight-average molecular weight 398.5, functional group 3, SC Organic Chemicals)

[0218] [ka]

[0219] (Radical polymerizable component: ethylenically unsaturated compound) C1: A compound represented by the following formula (C-1) (DPHA, Nippon Kayaku Co., Ltd.) C2: A compound represented by the following formula (C-2) (Viscoat #295, Osaka Organic Chemical Industry Co., Ltd.) C3: A compound represented by the following formula (C-3) (ABE300, Shin-Nakamura Chemical Co., Ltd.) C4: A compound represented by the following formula (C-4) (4-HBA, Mitsubishi Chemical Corporation)

[0220] [ka]

[0221] (Initiator: Photoinitiator (base generator and / or photoradical initiator)) D1: Compound (1) (Compound 1 prepared in Example 1) D2: Compound (2) (Compound 1 prepared in Example 2) D3: Compound (3) (Compound 1 prepared in Example 3) D4: Compound (4) (Compound 1 prepared in Example 4) D5: Compound (6) (Compound 1 prepared in Example 6) D6: Compound (7) (Compound 1 prepared in Example 7) D7: Compound (8) (Compound 1 prepared in Example 8) D8: Compound (9) (Compound 1 prepared in Example 9) D9: Compound (10) (Compound 1 prepared in Example 10) D10: Compound (11) (Compound 1 prepared in Example 11) D11: Compound (12) (Compound 1 prepared in Example 12) D12: Compound (13) (Compound 1 prepared in Example 13) D13: Compound (14) (Compound 1 prepared in Example 14) E1: Comparative compound 1 represented by the following formula E2: Comparative compound 2 (comparative compound prepared in Comparative Example 1) E3: Comparative compound 3 (comparative compound prepared in Comparative Example 2)

[0222] [ka]

[0223] (solvent) F1: gamma-butyrolactone F2: Dimethyl sulfoxide

[0224] [Evaluation method] The following evaluations 1 to 3 were carried out, and the results are shown in Tables 6 to 10. 1. Curability (low temperature heating) The compositions of each example and comparative example were applied to a SUS substrate with a dispenser to a thickness of 300 μm, and then irradiated with a high-pressure mercury lamp at 3,000 mJ / cm 2 2 (Cumulative light intensity in the wavelength range of 315nm to 400nm) was irradiated. After irradiation, the sample was left to stand at 60°C under atmospheric pressure for 1 hour, then palpated and evaluated according to the following criteria. +: No tuck. -:With tuck. The less tack there is, the more sufficiently cured the film is. The shaded areas are areas where no evaluation was performed.

[0225] 2. Curability (at room temperature) The compositions of each example and comparative example were applied to a SUS substrate with a dispenser to a thickness of 300 μm, and then irradiated with a high-pressure mercury lamp at 3,000 mJ / cm 2 2 (Cumulative light intensity in the wavelength range of 315nm to 400nm) was irradiated. After irradiation, the specimen was left to stand at 25°C under atmospheric pressure for 24 hours, and then palpated and evaluated according to the following criteria. +: No tuck. -:With tuck. The less tack there is, the more sufficiently cured the film is. The shaded areas are areas where no evaluation was performed.

[0226] 3.Storage stability The compositions of each Example and Comparative Example were each compounded in a 10 g scale into an amber screw tube. The viscosity (Pa·s) at 25°C was measured, and the samples were then stored at 23°C. After one week, the viscosity was measured again at 25°C. The viscosity increase rate (viscosity after storage / viscosity before storage × 100 (%)) was calculated and evaluated according to the following criteria. +: The viscosity increase rate is 110% or less. -: Viscosity increase rate is over 110%. The lower the viscosity increase rate, the better the storage stability.

[0227] [Table 6]

[0228] [Table 7]

[0229] [Table 8]

[0230] [Table 9]

[0231] [Table 10]

[0232] From the evaluation results of the Examples and Comparative Examples in Tables 6 to 10, it was confirmed that the compounds of the present disclosure have excellent storage stability and polymerization catalyst ability.

[0233] [Rating 2] The ability to dissolve the same mass of γ-butyrolactone at 25°C was confirmed. The results are shown in Table 11. In the following, "dissolved" means that the entire amount was dissolved when subjected to ultrasonic treatment for 30 minutes at 100 W and an oscillation frequency of 40 kHz. "Insoluble" means that insoluble matter was visible after the ultrasonic treatment. +:dissolution -: Insoluble

[0234] [Table 11]

[0235] As shown in Table 11, the compounds of the present invention have excellent solvent solubility.

[0236] [Rating 3] The photodecomposition behavior in acetonitrile solution was confirmed. The photodecomposition rates of compounds (1) to (6), (12), and (15) and comparative compounds 1 to 3 were measured using a quantum yield meter. -4 mol / L acetonitrile solution, and 10 mW / cm per second 2 The change in absorbance at λmax of various compounds due to light irradiation was observed. Exposure dose 3000mJ / cm 2 The photodecomposition rate was calculated from the change in absorbance at λmax of each compound at this point and the absorbance at λmax of each compound at the completion of photodecomposition using the following formula. The results are shown below.

[0237] Photolysis rate (%) = ((λmax absorbance when unexposed - exposure amount 3000mJ / cm 2 (λmax absorbance at the time of photodecomposition) / (λmax absorbance at the time of photodecomposition) × 100

[0238] [Table 12]

[0239] It can be determined that the higher the photolysis rate, the more efficiently the base is generated as a photobase generator. As shown in Table 12, the compounds of the present invention can generate a base with high efficiency, and this, combined with the high catalytic activity of the base having a quinuclidine skeleton itself, is presumably one of the reasons for the excellent polymerization catalytic activity.

Claims

1. A compound represented by the following general formula (1): 【Chemical 1】 (wherein Ar is an aromatic ring group represented by the following general formula (Ara1) or (Arb1), A is a group having a quinuclidine skeleton represented by the following general formula (A1) or (A2): B - is a monovalent anion, R 1 is a hydrogen atom, R 2 represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from the following Group I-1: The substituents substituting one or more hydrogen atoms in the substituted aliphatic hydrocarbon group, the substituted aromatic hydrocarbon ring-containing group, and the substituted heterocycle-containing group are atoms or groups selected from the following Group II-1: Group I-1: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R". Group II-1: halogen atoms, cyano groups, nitro groups, —CO—H, —OH, —SH, —NH 2 , —C(R′)═N—OH, —COOH, or —SO 3 H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different. 【Chemistry 2】 (wherein Y 1 is a sulfur atom; Y 2 is a single bond; Y 3 is CR 102 2 or NR 101 ; R 101 each independently represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from the following Group I-2: R 102 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group have been replaced with a divalent group selected from the following Group I-2: R 31 , R 32 , R 41 and R 42 each independently represent a halogen atom, a nitro group, a cyano group, —OR 121 , —COR 121 , —OCOR 121 , —COOR 121 , —SR 121 , —SOR 121 , —SO 2 R 121 , —NR 122 R 123 , —NR 122 COR 123 , or —CONR 122 R 123 . an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group are replaced with a divalent group selected from the following Group I-2: However, a plurality of R 41 may be bonded to each other to form a ring, and the ring is unsubstituted or has a substituent; R 121 , R 122 and R 123 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following Group I-2; when a plurality of R 121 , R 122 or R 123 are present, they may be the same or different, the aliphatic hydrocarbon group having the substituent, the aromatic hydrocarbon ring-containing group having the substituent, the heterocycle-containing group having the substituent, and the substituent substituting one or more hydrogen atoms in the ring formed by bonding a plurality of R 41 together are atoms or groups selected from the following Group II-2: a1 is an integer from 0 to 5, a2 is an integer of 0 to 4, b1 is an integer from 0 to 4, b2 is an integer from 0 to 3, * indicates the binding site. Group I-2: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-. Group II-2: a halogen atom, a cyano group, a nitro group, --CO--H, --OH, --SH, --NH.sub.2, --C(R').dbd.N--OH, --COOH, or --SO.sub.3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different. 【Chemistry 3】 (In the formula, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 111 , —COR 111 , —OCOR 111 , —COOR 111 , —SR 111 , —SOR 111 , —SO 2 R 111 , —NR 112 R 113 , —NR 112 COR 113 , —CONR 112 R 113 an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the following Group I-3, Or, two groups selected from R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are linked to each other to form a ring; X 11 and X 12 each independently represent a divalent group represented by —CR 201 R 202 —; R 111 , R 112 and R 113 , as well as R 201 and R 202 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group are substituted with a divalent group selected from the following Group I-3; when a plurality of R 111 , R 112 , R 113 , R 201 , and R 202 are present, they may be the same or different, a substituent substituting one or more hydrogen atoms in the substituted aliphatic hydrocarbon group, the substituted aromatic hydrocarbon ring-containing group, and the substituted heterocycle-containing group is an atom or group selected from the following Group II-3: * indicates the binding site. Group I-3: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group II-3: a halogen atom, a cyano group, a nitro group, --CO--H, --OH, --SH, --NH.sub.2, --C(R').dbd.N--OH, --COOH, or --SO.sub.3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different. 【Chemistry 4】 (In the formula, R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 111 , —COR 111 , —OCOR 111 , —COOR 111 , —SR 111 , —SOR 111 , —SO 2 R 111 , —NR 112 R 113 , —NR 112 COR 113 , —CONR 112 R 113 an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the following Group I-4, Or, two groups selected from R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are linked to each other to form a ring; X 21 and X 22 each independently represent a divalent group represented by —CR 201 R 202 —; R 111 , R 112 and R 113 , as well as R 201 and R 202 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocycle-containing group are substituted with a divalent group selected from the following Group I-4; when a plurality of R 111 , R 112 , R 113 , R 201 and R 202 are present, they may be the same or different; a substituent substituting one or more hydrogen atoms in the substituted aliphatic hydrocarbon group, the substituted aromatic hydrocarbon ring-containing group, and the substituted heterocycle-containing group is an atom or group selected from the following Group II-4: X 23 represents an oxygen atom; R′ and R″ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. * indicates the binding site. Group I-4: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-. Group II-4: a halogen atom, a cyano group, a nitro group, --CO--H, --OH, --SH, --NH 2 , --C(R')=N--OH, --COOH or --SO 3 H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group, and when there are multiple R's or R"s, they may be the same or different.

2. A compound described in claim 1, wherein R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18 and R 19 in general formula (A1) are hydrogen atoms or groups having 6 or less carbon atoms, and R 21, R 22, R 23, R 24, R 25, R 26 and R 27 in general formula (A2) are hydrogen atoms or groups having 6 or less carbon atoms.

3. The compound according to claim 1 or 2, represented by the following general formula (11): 【Chemistry 5】 (In the formula, A + , B - , R 1 and R 2 is the same as in general formula (1), R 31 , R 32 , a1 and a2 are the same as those in the general formula (Ara1).

4. Monovalent anion B - The compound according to any one of claims 1 to 3, wherein is a borate anion.

5. An initiator comprising a compound according to any one of claims 1 to 4.

6. A compound according to any one of claims 1 to 4; a curable component; and A composition comprising:

7. A cured product of the composition according to claim 6.

8. A method for producing a cured product, comprising the step of curing the curable component in the composition according to claim 6.

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